It acts as a lubricant in rubber molecules and can promote the relaxation of polymers, so that the chemical substances used in rubber processing are called softeners . Softeners are also called plasticizers, process oils, and compatibilizing oils. It is of course that softeners and compatibilizers play the role of lubricants, and the purpose of using them is to increase the volume of the complex and reduce the cost.
Softeners or plasticizers are divided into non-solvent type and solvent type . The vulcanized rubber plasticized by the non-solvent softener is full of resilience, but will migrate to the surface of the product when the amount exceeds the appropriate amount. In addition, when the solvent-based softener exceeds the appropriate amount, it acts as a solvent and cannot maintain the specific state of the product.
Softeners are roughly classified into mineral oils, vegetable oils and synthetics according to their raw materials. Petroleum softeners represented by mineral oils have a wide range of products, ranging from paraffin oils with low affinity for rubber to high aromatic oils with high affinity for rubber. They are used not only as processing oils, but also as fillings for oil-extended SBR Oil is consumed in large quantities. In addition, coal tar products are almost all composed of high aromatic hydrocarbons, which have good compatibility with rubber and can improve processing performance. However, due to the high embrittlement temperature, there are certain problems for products used at low temperatures, and it may also affect vulcanization.
Pine oil, pine tar, etc. obtained from pine trees are important softeners and tackifiers for natural rubber. Because of their acidity, they can delay vulcanization and are effective in reducing the scorch of carbon black compound rubber. But because the vulcanization of synthetic rubber is generally slower than that of natural rubber, pay attention to it when using it. In addition, the compatibility of natural oils and rubbers is not great, but they have a lubricating effect, and some can be used in vulcanization systems by further reacting with alkaline accelerators and zinc oxide. As a vulcanized grease, ointment can be widely used as an auxiliary agent for rubber calendering and extrusion operations.
Synthetic organic compounds, especially ester plasticizers, are mainly used in the compounding of nitrile rubber. For this, please refer to the plasticizer item in the previous chapter.
10.1 mineral oil softener (Mineral oil softeners)
10.1.1 petroleum softening agent : process oil (Petroleum softener: Process oil)
Due to the discovery of the low-temperature polymerization of SBR, high molecular weight synthetic rubber was produced. With the addition of high-boiling petroleum fractions to obtain oil-extended SBR, oil softeners have attracted attention. Therefore, the oil used in the manufacture of oil-extended rubber is called extender oil, and the oil mixed into the rubber during kneading is called process oil.
There are three classification methods for operating oils. Here is a brief introduction to the commercial products of paraffin and aromatic operating oils.
(1) Paraffinic oil
This series of operating oils are excellent in extrusion, low temperature performance, pollution resistance, aging resistance, etc., but the compatibility and processing performance are slightly poor, and the exudation is also poor. But it has good compatibility with butyl rubber, EPM and EPDM. The technical indicators of Kobe Chemical Company in Japan are as follows:
Specific gravity ( 15/4℃) 0.8661～0.8768, viscosity (cst, 37.8℃ ) 21.9～389.0, aniline point (℃ ) 94.4～142.0, pour point (℃ ) -12.5, flash point (℃ ) 200～295, viscosity specific gravity Constant 0.794～0.814, hue (ASTM ) L0.5, ring analysis (%) C A 0～2.5, C N 28.0～36.0, C P 64～72.0.
(2) naphthenic oil (naphtenic oil)
The operating oil of this series is between the paraffinic and aromatic operating oils. It has a wide range of applications. It can produce a complex that has a balance of pollution resistance, low temperature performance, processing performance, and aging resistance. It can also improve the performance of vulcanized rubber. Tensile strength, elasticity, and elongation also have a good effect on crack resistance and abrasion resistance. The technical indicators of Kobe Chemical Company in Japan are as follows:
Specific gravity ( 15/4℃) 0.9083～0.9471, viscosity (cst, 37.8℃ ) 19.02～310.00, aniline point (℃ ) 42.2～85.0, pour point (℃ ) -27.5～-10.0, flash point (℃ ) 160～230 , Viscosity specific gravity constant 0.863～0.932, hue (ASTM ) L1.0～3.0, ring analysis (%) C A 14.0～31.0, CN 30.0～43.0, C P 28～52.
(3) Aromatic oil
This series of operating oils has good compatibility and exudation resistance, so the processing performance is very excellent, but the low temperature performance, pollution resistance, heat generation, etc. are slightly poor. The technical indicators of Kobe Chemical Company in Japan are as follows:
Specific gravity ( 15/4℃) 0.9780～1.0190, viscosity (cst, 100℃ ) 5.1～24.6, aniline point (0℃ ) 2.0～30.0, pour point (℃ ) -35.0～5.0, flash point (℃ ) 160～250 , Viscosity specific gravity constant 0.949～1.065, color tone (ASTM ) D8.0, L2.0, ring analysis (%) C A 41.0～45.0, CN 17.0～36.5, C P 22.0～39.5.
10.1.2 Special process oil
Specific gravity ( 15℃) 0.860, viscosity (40℃ ) 28cst, aniline point 55℃ , pour point -40℃ , hue ( ASTM ) L0.5. Used in natural rubber, SBR, CR, PN (polynorbornene), especially as a non-adhesive and non-polluting softener for CR, with excellent compatibility and processability.
10.1.3 ethylene with 2- olefin copolymer (cooljgomer of ethylene and 2-olefin )
( 1 ) Colorless and transparent liquid. The specific gravity is 0.826～0.850. The acid value is below 0.01. Ash content below 0.01. Hue (APHA ) 5. Hydrocarbon synthetic oil without polar groups. No volatilization, low pour point, high flash point and combustion point, excellent thermal stability and oxidation stability.
( 2 ) It is used as a softening agent and processing aid in the fields requiring heat resistance, cold resistance and volatility resistance.
10.1.4 Paraffin wax
The separated crude wax oil is removed from petroleum, and it is a crystalline substance that is washed, decolorized and refined. FDA qualified product.
( 1 ) Appearance: white waxy solid. The specific gravity is 0.87～0.93 (25℃ ). The melting point is 45～69℃ . Soluble in gasoline, benzene, chloroform, carbon disulfide, etc., but insoluble in water.
( 2 ) It is used for natural rubber and synthetic rubber. It has the ability to prevent gas and water permeability, can improve electrical insulation, and give products luster. But it is easy to bloom.
10.1.5 liquid paraffin (liguid paraffin)
After the crude oil is distilled under normal pressure and vacuum, the unsaturated components, aromatic components and sulfur components are removed.
( 1 ) It is colorless, tasteless and odorless liquid. It has relatively stable effects on light, heat and acid, and does not react chemically to neutral substances.
( 2 ) It is rarely used as a softener for rubber, but also as a release agent, internal lubricant, and extrusion aid for plastics. The German Food Law recognizes rubber products for use in contact with food.
10.1.6 White Oil (white oil)
A particularly highly refined colorless and odorless petroleum fraction. FDA qualified product. Widely used as a softener for rubber, plastics, adhesives, etc.
10.1.7 Vaseline (petrolatum)
A jelly-like semi-solid wax made from petroleum. FDA qualified product.
( 1 ) There are many varieties of characters. The melting point is 44.4～51.7℃ . Viscosity ( SUS, 98.9℃ ) 35～90.
( 2 ) It can be used as a softener and lubricant for rubber, plastic and adhesive.
10.1.8 Petroleum sulfonate (petro leum sulfonate)
When petroleum fractions are refined from sulfuric acid, the by-product hydrocarbon sulfonates. FDA qualified product. Used as rubber softener, also used as emulsifier, dispersant, lubricant, rust inhibitor.
10.1.9 Asphalt (gilsonite; natural asphaltum)
A kind of natural asphalt, formed by natural evaporation of some non-paraffin petroleum components, and is produced in North America, such as California, Mexico, and Cuba.
( 1 ) Character black coal-like substance. The texture is brittle, and the section is conchoidal. The specific gravity is 1.04～1.076. The softening point is 126～149℃ . Soluble in carbon disulfide, carbon tetrachloride, mineral spirits, etc. FDA qualified product.
( 2 ) In addition to reducing the cost of rubber products, it can also provide a softening effect and improve water resistance and electrical insulation.
10.1.10 Asphalt ( Petroleum Asphalt)
It is made from non-paraffin distillation residues, and it is divided into straight-run asphalt and blown asphalt. The former is made directly from the distillation residue, and the latter is made by blowing the distillation residue into air. FDA qualified product.
( 1 ) Character black solid. When the amount of paraffin wax increases, it fluoresces. The specific gravity is 1.01～1.05. The softening point is 50～150℃ . The flash point is 210～220℃ . There are various penetrations.
( 2 ) The effect on natural rubber and synthetic rubber is the same as that of asphalt.
10.1.1 a petroleum resin ( Petroleum Resin)
Crude gas oil decomposed by steam cracking contains highly unsaturated hydrocarbons, and its polymer is petroleum resin. The main components of the resin are styrene, vinyl toluene, and indene.
( 1 ) The molecular weight of traits is 600 ～3000 . The melting point is 60～125℃ . The specific gravity is 0.970～0.975. The flash point is 260℃ . Good compatibility with rubber and plastic. FDA qualified product.
( 2 ) It has the function of softening natural rubber and synthetic rubber and helping to disperse the filler. It is especially suitable for butyl rubber. It has little effect on tensile strength and fixed elongation stress, and can improve hardness, tear strength and elongation. It is also used in adhesives, coatings, varnishes, etc.
10.1.12 Coumarone - indene resin ( coumarone-indene resin )
See section Tackifiers.
10.2 vegetable oil-based softener ( Vegateble Oil Softeners )
10.2.1 castor oil ( Castor Oil )
( 1 ) Odorless or slightly odorous light yellow to light brown oily liquid. The specific gravity is 0.96. Freezing point -10～-21℃ . The iodine value is 83～89. Saponification value is 178～182. It is unsaturated oil. Soluble in ethanol, insoluble in gasoline, FDA qualified product.
(2) It has a softening effect on natural rubber and synthetic rubber. But the solubility of vulcanized rubber is low, and sometimes it shows signs of bleeding. Generally not used, but can be used as cold-resistant plasticizer.
10.2.2 cotton seed oil ( Cotton Ceed Oil )
( 1 ) Properties: light yellow to dark red oily liquid. The specific gravity is 0.915～0.932. Freezing point -6～-1℃ . The iodine value is 88～128. The saponification value is 190～198. It is a semi-drying oil. Soluble in ether, benzene, gasoline, etc., slightly soluble in ethanol, FDA qualified product.
(2) Function: Used for natural rubber and synthetic rubber, it can improve elongation and softness, so it is easier to use. No adverse effects on vulcanized products.
10.2.3 linseed oil ( linceed Oil )
( 1 ) Properties: Amber to brown with special smelly dry oil. The specific gravity is 0.925～0.929. Freezing point -18～-27℃ . The iodine value is 170～188. Saponification value is 186～195. Soluble in chloroform, benzene, carbon disulfide, gasoline, etc. FDA qualified product.
(2) The softening effect is great, but there is a tendency to age the product.
10.2.4 rapeseed oil ( Rape Ceed Oil )
( 1 ) It is light yellow semi-dry oil with bitter taste. The specific gravity is 0.9132～0.9168. The freezing point is about 0°C . The iodine value is 94～106. Saponification value is 169～179. FDA qualified product.
(2) It has a great softening effect on natural rubber and synthetic rubber and can be widely used.
10.2.5 soybean oil ( Soya bean Oil )
( 1 ) Properties: light yellow dry oil with slight smell. The specific gravity is 0.924～0.929. Freezing point -7～8℃ . The iodine value is 123～137. The saponification value is 190～193. FDA qualified product.
(2) It has a plasticizing effect on natural rubber and synthetic rubber, but it has a tendency to ooze onto the surface.
10.2.6 Palm Oil ( Palm Oil )
( 1 ) Properties: Red solid resin with slight odor. The specific gravity is 0.9917～0.9922. The melting point is 30～45℃ . The iodine value is 44～56. The saponification value is 196-210. Soluble in ethanol, ether, chloroform, carbon disulfide. There is fragrance and sweetness. FDA qualified product.
(2) It has a good softening effect on natural rubber and synthetic rubber.
10.2.7 Coconut oil ( coconut oil )
( 1 ) Appearance: white to light yellow waxy solid with special smell. The specific gravity is 0.9115. The melting point is 20～28℃ . The iodine value is 8～9.5. The saponification value is 250～258. FDA qualified product.
(2) It has a good softening effect on natural rubber and synthetic rubber.
10.2.8 peanut oil ( Peanut Oil )
( 1 ) Non-drying oil with light yellow to greenish properties. The specific gravity is 0.915～0.921. The iodine value is 86～98. The saponification value is 188～197. Freezing point -5～3℃ . Insoluble in water and alkali, soluble in benzene and gasoline.
( 2 ) The softening effect on natural rubber and synthetic rubber is great, and the pollution is small. FDA qualified product.
10.2.9 Wood wax ( japan wax; haze wax )
There are fats derived from the mesocarp of the fruits of lacquer and wood wax. It is not a wax in terms of chemical composition.
( 1 ) The main component of the character is the glyceride of soft value acid, which is yellow to white solid. The specific gravity is 0.97～1.0. Melting point is 48～54℃ . The saponification value is 201～237. Soluble in ethanol and benzene.
( 2 ) It is sometimes used as a softener and brightener for hard rubber.
10.2.10 Rosin ( rosin )
The residue after removing turpentine from turpentine by steam distillation, and then refining it, or it can be obtained by solvent extraction by removing water from pine bark. The former is called gumrosin (gumrosin), the latter is called wood rosin ( wood rosin ). Rosin is mainly produced in the United States, France, Germany, Portugal, and China.
( 1 ) Properties: light yellow to dark brown transparent block. The specific gravity is 1.045～1.086. The softening point is 70～80℃ . Soluble in ethanol, methanol, ether, benzene, acetone, turpentine. FDA qualified product, approved by German Food Law.
( 2 ) It can be used as softener and tackifier of natural rubber, styrene butadiene rubber, etc. It can slightly delay vulcanization and reduce tensile strength, but it can increase elongation and improve resistance to deflexion. For rosin derivatives, please refer to the chapter on tackifiers. In addition, uneven rosin acid soap can be used as an emulsifier in synthetic rubber manufacturing.
10.2.11 Pine -oil and dipentene ( pine-oil and dipentene )
After the crude turpentine is fractionated from turpentine crude oil, the distillate that is fractionated below about 360°C is called crude pine oil, and the distillate that is fractionated below 260°C after chemical treatment is called sesquiterpenes The oil, followed by the distillate fractionated below 360°C, is called refined pine oil. In addition, the dipentene is dipentene as the distillate of crude turpentine after chemical treatment at 178-210 °C .
( 1 ) Properties Dipentene is a light yellow transparent liquid with a specific gravity of 0.850～0.880. Sesquiterpene oil is a light yellow and slightly viscous liquid with a specific gravity of 0.925 to 0.935. Pine oil is a dark brown transparent liquid with a specific gravity of 0.900～0.930. FDA qualified product.
( 2 ) It is mainly used as a solvent for coatings, but also as a solvent for natural rubber, styrene-butadiene rubber, etc. or as a plasticizer during rolling operations. It has a considerable effect on improving the flexibility resistance of sulfides. In addition, it is also used as a softener for reclaimed rubber.
10.2.12 Pine-tar contained softeners ( pine-tar contained softeners )
When turpentine crude oil is distilled, the refined substance of heavy oil remaining in the still is called pine tar. Pine tar oil has excellent softening effect and dispersion effect as a rubber softener, and can give adhesion.
( 1 ) Characters are dark brown liquid. The specific gravity is 0.980～1.020. The acid value is 35～60. Viscosity (Ridewood No. 1, 80°C ) 150 to 250 seconds.
(2) It acts as a softener for high-grade rubber.
10.2.13 Tall oil ( tall oil )
In the production of kraft pulp, the resinous fatty substances in the wood are separated as sodium salt, and then decomposed by acid. It is composed of fatty acids and resin acids.
( 1 ) Light brown to dark brown oily liquid with special odor. Unstable traits. The acid value is 120～180. The iodine value is 120～170. FDA qualified product.
(2) It is widely used because it can give natural rubber and synthetic rubber an excellent softening effect.
10.2.14 refined tall oil ( refined tall oil )
It is refined from crude tall oil, with less resin and saponification, and higher acid value.
( 1 ) Properties: brown viscous to black viscous. The acid value is 10-25. Viscosity (Ridewood No. 1, 80°C ) 100 to 300 seconds.
(2) Act as a regeneration and softening agent for natural rubber and synthetic rubber.
10.3 Ointment ( Rubber-subsitute; Factice )
Ointment is used as a softener, processing aid, and compatibilizer at the beginning of the rubber industry. It has the characteristics of giving rubber products flexibility, and this flexibility hardly changes with temperature. Ointment is an indispensable compounding agent for soft rubber. The ointment is effective in preventing the rubber from sticking to the roller during mixing, improving the operability during calendering and extrusion, preventing the shrinkage of unvulcanized rubber and preventing mold collapse. In addition, it is also effective in promoting vulcanization and preventing blooming. It can be used in NR, SBR , NBR , CR , IIR , BR , IR , EPDM, etc. White ointment is an indispensable compounding agent for making erasers. Sulfur-sulfurized rapeseed and soybean oil are FDA qualified products. The German Food Law recognizes rubber products used in food contact.
10.3.1 Black ointment ( brown factice; brown subsitute )
Brown elastomer (flaky or crumb powder) made by heating and vulcanizing oxidized vegetable oil (mainly rapeseed oil) with sulfur, mainly used for black rubber products. The specific gravity is 1.01～1.05 . The acetone extraction is 10 to 50% . Contains 0.6 to 3.0% of free sulfur . The ash content is below 0.1 to 0.2% .
10.3.2 White factice ( white factice; white subsitute )
Vegetable oil is a white to slightly yellow product made by sulfur chloride vulcanization at room temperature. Usually calcium carbonate is added to prevent deterioration. Among various vegetable oils, rapeseed oil can give the driest product. In addition, there are also white ointments containing mineral oil. The specific gravity is 1.00～1.32 . Acetone extract 2 ~ 35% . Free sulfur 0.1 ~ 1.0% . The ash content is 0.5 to 1.0% .
10.3.3 Butter paste ( amber factice; semi-translucent factice )
Vegetable oil is vulcanized with sulfur chloride to obtain amber flakes. Mainly used for transparent rubber products. Compared with white ointment, it has less delay effect on organic accelerator. The specific gravity is 0.95～1.01 . Acetone extract 12 ~ 59% . Free sulfur 0.1 ~ 2.0% . The ash content is 0.5 to 1.0% .
10.3.4 Other ointment ( other factice )
The commercial products of ointment include light-colored and non-delayed vulcanized varieties, soft varieties with less free sulfur, and varieties with fatty acid glycerides as raw materials. In addition, there are special products for synthetic rubber. New form of ointment.
10.4 Fatty acids and fatty acid salts ( Fatby acids and theit salts )
As mentioned in the accelerator chapter of this book, stearic acid can improve the dispersibility of carbon black, etc. and improve the wear resistance of vulcanized rubber, and can be used as a softener for alkaline reclaimed rubber. In addition, lauric acid has a greater softening effect on natural rubber and synthetic rubber. Here is an introduction to fatty acids and their salts.
10.4.1 Ricinoleic acid ( ricinoleic acid )
( 1 ) The characters are contained in castor oil. The specific gravity is 0.940 . Melting point 4 ~ 5 ℃ . Soluble in ethanol, propanol, ether and chloroform. FDA qualified product.
(2) It is used for natural rubber and synthetic rubber. It can improve the operability of rolling and extrusion, and can improve the flexibility resistance of vulcanized rubber. Like stearic acid, it is also used as a vulcanization accelerator.
10.4.2 palmitic acid ( palmitic acid )
( 1 ) Appearance is white crystal. The proportion is 0.85 . The melting point is 63 ～64 ℃ . Soluble in ether, benzene, chloroform, insoluble in petroleum ether, insoluble in water. FDA qualified product.
(2) It is used for natural rubber and synthetic rubber, and it has the same effect as stearic acid. It can slightly increase the viscosity, but the aging resistance of its products is worse than that of stearic acid.
10.4.3 Myristic acid ( myristic acid )
( 1 ) Appearance is white crystalline solid. The proportion is about 0.86 . The melting point is 54 ℃ . Insoluble in cold ethanol and cold ether. FDA qualified product.
(2) It is used for natural rubber and synthetic rubber, and its effect is basically the same as stearic acid.
10.4.4 Barium stearate ( barium stearate )
( 1 ) Appearance is white powder. The density is 1.145 . The melting point is above 220 ℃ .
(2) It is used for natural rubber and synthetic rubber, and has almost no effect on vulcanization. Excellent lubricity and good heat resistance. It has a synergistic effect with zinc soap, zinc compound and epoxide.
10.4.5 calcium stearate ( Calcium stearate )
( 1 ) Appearance is white powder. The melting point is about 150 ℃ . Non-toxic.
(2) It has a softening effect on natural rubber and synthetic rubber, and has almost no effect on vulcanization. Excellent lubricity. It has a synergistic effect with zinc soap or epoxide. It has good operability and resistance to vulcanization, but large amounts will cause scaling. It is used for non-toxic compounding in food packaging.
10.4.6 Magnesium Stearate ( Magnesium stearate )
( 1 ) Appearance is white powder. The density is 1.028 . The melting point is about 140 ℃ . Odorless. Slightly soluble in water, soluble in hot ethanol.
(2) It has a softening effect on natural rubber and synthetic rubber, and an activation effect on vulcanization.
10.4.7 zinc stearate ( Zinc stearate )
( 1 ) Appearance is white powder. The density is 1.05 ~ 1.10 . The melting point is about 120 ℃ . Cheap and non-toxic. It can be used in combination with barium soap for vulcanization resistance, and it can be used in food packaging with calcium soap. Used together with barium compounds can improve the initial coloring, precipitation and scaling. In addition, it is also widely used as dusting powder, lubricant and release agent for rubber products.
10.5 Special blend softener (Speciality blended softeners)
10.5.1 Mixture of higher alcohol fatty acid ester and synthetic oil
( 1 ) Transparent liquid without discoloration. The specific composition is not clear, and the density is 0.87 (15°C). Viscosity 60cst (40℃). Aniline point 70℃ . Color (ASTM) L0.5.
(2) It is used as a transparent compound for natural rubber, styrene butadiene rubber and butadiene rubber.
10.5.2 Water-soluble higher alcohol fatty acid esters
The specific ingredients are unknown. It has good compatibility with natural rubber latex and synthetic rubber latex and can soften latex. The pour point is 0°C .
10.6 rubber processing aid with a special fitting (Speciality processing aids for ruubers)
There are many types of special processing aids for rubber, but the specific ingredients are not clear. Only select several translations for reference.
10.6.1 Aliphatic resin mixture
Amber flakes. The molecular weight is below 2000 . Density 1.0 . The softening point is about 100°C . Soluble in aliphatic, aromatic and chlorinated carbon solvents. It can be used as a leveling agent, it does not harden even during vulcanization, and the hardness of sulfide is not lower than that of mineral oil.
10.6.2 Higher fatty acid zinc salt mixture
Light yellow scaly. Density 1.1 . The melting point is 75～85℃ . Ash content is 20%. Soluble in natural rubber, synthetic rubber, aromatic solvents, polar solvents. It can plasticize the rubber compound, help the dispersion of the compounding agent, and shorten the mixing time. Especially when used in natural rubber, it can prevent the reversion of vulcanization, so it can improve the physical properties of vulcanized products (tensile performance, tear resistance, dynamic performance). The compounding rubber can be used for continuous vulcanization, injection molding and transfer molding. Comply with German Food Law.
10.6.3 Resiny metal salt mixture with soluble phase glue
Dark brown viscous substance. The density is about 1.0 . The softening point is 50 ℃ . Processing aids suitable for polymer blending, used with NR, IR, SBR, BR, EP, NBR, etc. Excellent compatibility, it is effective for shortening the mixing cycle, improving the adhesion of unvulcanized rubber, and reducing extrusion expansion.
10.6.4 Special ester wax
Light yellow particles. Melting point 52℃ . The volatile content is below 6.0%. The ash content is below 1.5%. It can reduce the viscosity of the rubber material during processing, and can reduce mechanical torque and electronic consumption. In addition, it can improve the wetting of the interface between carbon black and unvulcanized rubber to facilitate the dispersion of carbon black. It is effective in preventing scorching and thermal aging of the rubber compound, and improving the mold release and surface smoothness of the product. Suitable for chloroether rubber, etc.
Two, rubber plasticizer
The plasticizer can give the polymer plasticity, and can help the compounding agent to mix and disperse, facilitate the molding operations such as calendering and extrusion, and increase the viscosity of the unvulcanized rubber for easy molding. There is generally no obvious distinction between plasticizers and softeners, process oils, extenders, etc.
Polymers that can be formulated with plasticizers include polyvinyl chloride resin, vinyl acetate resin, polyvinyl acetal, polyvinyl formal, nitrocellulose, acetyl cellulose, synthetic rubber, and the like. Especially for polyvinyl chloride resins, most of them can be added with a plasticizer of 40-50% of the weight of the resin and act as a soft elastomer at room temperature. Therefore, the softening effect of the plasticizer is extremely important.
The plasticizer industry was created and grown with the development of cellulose. In World War II, with the rapid growth of polyvinyl chloride resin, it reached the sales of hip-range compounds. However, the most widely used and most consumed in industry are dibasic acid esters, especially phthalate esters, whose market share is about 80% of the total output of plasticizers.
In addition, as a plasticizer, the following conditions should be met: ( 1) High speed-increasing efficiency, even a small amount can improve plasticity and give sufficient flexibility; (2) Speed-increasing speed; (3) Good compatibility; (4) Low volatility; (5) No transfer; ⑹No loss of flexibility at low temperatures; ⑺Cannot be extracted with water, oil, grease, etc.; ⑻Good heat resistance, light resistance, and high chemical stability; ⑼Good electrical insulation; ⑽Flame retardant; ⑾Pollution resistance Good; ⑿ has antibacterial properties; ⒀ should be colorless, tasteless, odorless, non-toxic; ⒁ cheap and so on. However, there may not be a plasticizer that can meet the above-mentioned requirements. Therefore, two or more plasticizers are mixed and used while seeking to reduce the price. The plasticizer with large plasticizing effect and large amount is called the main plasticizer, and the plasticizer that plays an auxiliary role is called the auxiliary plasticizer.
9.1 phthalic acid derivatives ( Phthalicacid derivalives )
9.1.1 dimethyl phthalate ( dimethyl phthalate; the DMP )
( 1 ) Colorless and transparent liquid. The molecular weight is 194 . The specific gravity is 1.192 ( 20 ℃ ). The flash point is 149°C and the boiling point is 282°C ( 760mm Hg). Freezing point 0℃ . Color ( APHA) below 30. Viscosity 22CP (20°C). FDA qualified product (only for adhesives).
( 2 ) It is used to plasticize natural rubber, synthetic rubber, cellulose resin, and vinyl resin, but its use is restricted due to its high volatility. It can be used for nitrocellulose to give plastics with good light resistance. In addition, it has no effect on rubber vulcanization and can give cold resistance.
9.1.2 Diethyl phthalate (DEP )
( 1 ) Colorless liquid with slight fragrance. The molecular weight is 222 . The specific gravity is 1.120 ( 20 ℃ ). The flash point is 153℃ , the boiling point is 298℃ ( 760mmHg). Freezing point -40℃ . Color ( APHA) below 30. The viscosity is 13CP (20°C). FDA qualified product (paint).
( 2 ) It is used to plasticize natural rubber, synthetic rubber, cellulose resin and vinyl resin, but its use is restricted due to its high volatility. It is especially suitable for nitrocellulose, with excellent toughness, elongation and light resistance, and can produce odorless products. It is also used in vinyl acetate adhesives.
9.1.3 dibutyl phthalate ( dibuthyl phthalate; the DBP )
( 1 ) A colorless oily liquid with a slight odor. The molecular weight is 278 . The specific gravity is 1.048 ( 20 ℃ ). The flash point is 170℃ , and the boiling point is 340℃ ( 760mmHg). Freezing point -35℃ . Color ( APHA) below 25. The viscosity is 20CP (20°C). FDA qualified product (cellophane, adhesive).
( 2 ) It can plasticize natural rubber, synthetic rubber, cellulose resin and vinyl resin. It is also one of the most important plasticizers of nitrocellulose paint. It has excellent compatibility and plasticizing efficiency for polyvinyl chloride resin, and has shortcomings in volatility and oil resistance, but it is cheap and widely used as the main plasticizer. Also. The compatibility with vinyl acetate resin is also good, and it can be used to make coatings, adhesives, etc.
9.1.4 Dioctyl phthalate ( dioctyl phthalate; DOP )
( 1 ) A light yellow oily clear liquid with a special smell. The molecular weight is 391 . The specific gravity is 0.9861 ( 20 ℃ ). Boiling point is 386°C ( 760mmHg). Freezing point -53℃ . Color ( APHA) below 30. The viscosity is 80CP (20°C). FDA qualified products (rubber products, adhesives, etc.).
( 2 ) It is used to plasticize synthetic rubber, vinyl resin and cellulose resin. It is one of the most used plasticizers. It has good compatibility with PVC, and has a good balance of flexibility, cold resistance, light resistance, aging resistance, volatility, migration resistance, extraction resistance, electrical properties, etc., so it is widely used as the main standard Plasticizer. Also used for plastisol. No effect on rubber vulcanization.
9.1.5 Di-n-octyl phthalate ( di-n-octyl phthalate; n-DOP )
( 1 ) Oily, clear liquid with a slight smell. The molecular weight is 391 . The specific gravity is 0.978 ( 20 ℃ ). The flash point is 219℃ . The boiling point is 230°C ( 4mmHg). The freezing point is below -25℃ . Color ( APHA) below 30. The viscosity is 25cts (30°C). FDA qualified products (rubber products, adhesives, etc.).
( 2 ) The isomer of DOP . Plasticizer for synthetic rubber, vinyl resin and cellulose resin. Compared with DOP, it has better cold resistance, weather resistance, volatility resistance, and viscosity stability of the plastisol. The plasticizing efficiency is the same as DOP , but the electrical insulation is slightly worse.
9.1.6 phthalate, diheptyl ( diheptyl phthalate; DHP )
( 1 ) The character is clear and liquid. The molecular weight is 362 . The specific gravity is 0.995 ( 20 ℃ ). The flash point is 225℃ . Freezing point- below 46℃ . The viscosity is 44.7cp (30°C). Color (APHA) 20.
( 2 ) Act as a plasticizer for polyvinyl chloride resin. Since the molecular weight is slightly lower than DOP , the heating loss is larger, but it has excellent mixing properties, good plasticization efficiency, and cold resistance. Other physical properties are the same as DOP , which is used to replace DBP which is a more volatile plasticizer .
9.1.7 phthalate, diisodecyl phthalate ( diisodecyl phthalate; DIDP )
( 1 ) Oily, clear liquid with a slight smell. The molecular weight is 446 . The specific gravity is 0.961 ~ 0.969 ( 25 ℃ ). The flash point is 221 ~ 136 ℃ . Boiling point is 420℃ ( 760mmHg). The freezing point is below -20℃ . Color ( APHA) below 30. The viscosity is 83cp (20°C). FDA qualified products (rubber products, sealing rings, adhesives, etc.).
( 2 ) It acts as the main plasticizer for synthetic rubber, vinyl resin and cellulose resin. Due to the high molecular weight, the compatibility is worse than the plasticizer DOP , but it has low volatility, migration resistance, extraction resistance, and electrical insulation. However, cold resistance and oil resistance are slightly worse. Coloring occurs when heated, but this can be prevented by using it in combination with an antioxidant. There are also modified products with bisphenol A added .
9.1.8 Phthalate undecyl ( diundecyl phthalate; the DUP )
( 1 ) The character is clear and liquid. The molecular weight is 474 . The density is 0.953g/cm 3 ( 20℃ ). Freezing point- below 12℃ . The flash point is 252℃ . Boiling point is 280℃ ( 7mbor).
( 2 ) Act as the main plasticizer for PVC resin. Has particularly good cold resistance and low volatility. Used for PVC wire coating and car interior products.
9.1.9 Di-heptyl undecyl phthalate ( di- ( heptyl, undecyl phthalate )
( 1 ) The character is clear and liquid. The molecular weight is 414 . The density is 0.971g/cm 3 ( 20℃ ). Freezing point- below 57℃ . The viscosity is 40 mpas (25°C). The flash point is 230℃ . The boiling point is 275°C ( 7mbor).
( 2 ) It is a general plasticizer for PVC resin. It is used in applications that require low-temperature flexibility, volatility, and strict paste viscosity stability, instead of plasticizer DOP .
9.1.10 phthalate, butyl benzyl phthalate ( butyl benzyl phthalate; BBP )
( 1 ) Properties, colorless, odorless, oily, clear liquid. The molecular weight is 312 . The specific gravity is 1.119 ( 20 ℃ ). The flash point is 185℃ , and the boiling point is 370℃ ( 760mmHg). The freezing point is below -35℃ . FDA qualified products (including food packaging), approved by the German Food Law.
( 2 ) It acts as a plasticizer for natural rubber, synthetic rubber, vinyl resin, and cellulose resin. Low volatility, good heat resistance and light resistance. Especially for polyvinyl chloride, it can provide excellent processability, good oil extraction resistance, and the prepared sheet has good pollution resistance and abrasion resistance.
9.1.1 1 diisononyl phthalate ( diisononyl phthalate; DINP )
( 1 ) Properties are almost colorless and transparent liquid. The molecular weight is 419 . The specific gravity is 0.970 ( 25 ℃ ). The boiling point is 230～238℃ ( 5mmHg). The flash point is 219℃ . Freezing point- 25℃ . The viscosity is 78～120cp (20℃).
( 2 ) The role is mainly used as a plasticizer for polyvinyl chloride resin. Can give good light resistance, heat resistance, aging resistance, electrical insulation, low volatility, but not so good cold resistance. The plasticization efficiency is worse than that of the plasticizer DOP . It can also be used for nitrile rubber and cellulose resin.
9.1.12 Di-n-alkyl phthalate ( di-n-alkyl phthalate )
(1) The molecular weight of traits is 391 . The volatility is lower than the plasticizer DOP . It has excellent cold resistance and weather resistance, and is used for electric wires and agricultural films. Good viscosity stability, also used for plastisol. Also. When used in films, sheets, and artificial leather, it can save cold-resistant plasticizer DOA and plasticizer DOS .
9.1.13 Alkyl benzyl phthalate (ABP )
( 1 ) The properties are clear and oily liquid. The molecular weight is 368 . The specific gravity is 1.070 ( 25 ℃ ). Boiling point is 252℃ ( 10mmHg). Freezing point -45℃ . Viscosity 52cst (25°C).
( 2 ) It acts as a plasticizer for polyvinyl chloride resin and acrylic paint. Although it has the performance matching with low molecular weight polyester plasticizer, it still maintains the advantages of low molecular weight plasticizer. Especially suitable for PVC film, board, artificial leather, paste, foam, acrylic resin paint.
9.1.14 phthalic acid dialkyl esters ( dialkyl phthalate )
( 1 ) The proportion of traits is 0.954 to 0.964 . The acid value is below 0.1 . The ester value is 240 ~ 254 .
( 2 ) It acts as a plasticizer with heat resistance and fogging resistance. The heat resistance is between the plasticizer DIDP and trimellitate plasticizer. Suitable for artificial leather, wires, plates, and extruded products.
9.1.15 phthalate, dibutyl ester group ( dibutoxyethyl phthalate; DBEP )
( 1 ) The appearance is almost colorless and clear liquid. The molecular weight is 366 . The proportion is 1.06 . Viscosity 46cp (25°C). Color 2. The flash point is 266℃ . Freezing point- 50℃ .
( 2 ) Act as a plasticizer for synthetic rubber. No effect on vulcanization.
9.1.16 phthalate, dibutoxyethyl ( dibutoxye phthalate thoxyethyl- )
( 1 ) Transparent liquid in appearance. The specific gravity is 1.072 (25℃) . The acid value is 0.71 . The flash point is 204℃ . Freezing point- 41℃ .
( 2 ) It acts as a plasticizer for synthetic rubber and plastics.
9.1.17 dimethyl cyclohexyl phthalate ( dimethyl cyclohexyl phthalate )
( 1 ) Liquid with freezing point- 40℃ . The viscosity is 15000～25000mPa·s.
( 2 ) It is used as a plasticizer for coatings, automotive undercoats, sealants, and acrylic coatings.
9.1.18 acid ethyl phthaloyl ethyl ( Ethy phthalyl ethyl glycolate; EPEG )
( 1 ) It has a slight odor and colorless liquid. The molecular weight is 280 . The specific gravity is 1.184 ( 20 ℃ ). The flash point is 193℃ . Boiling point is 310℃ ( 760mmHg). Freezing point +20℃ . The viscosity is 63cp (25°C). FDA qualified product (coating, adhesive).
( 2 ) It acts as a plasticizer for synthetic rubber, vinyl resin and cellulose resin. Good light stability and hard to volatilize. It is especially suitable for acetyl cellulose, which can give the film different light resistance, moisture resistance and elasticity. It has good compatibility with polyoxyethylene and vinyl acetate resins.
9.1.19 butyl phthalyl butyl glycolate ( butyl phthalyl butyl glycolate; BPBG )
( 1 ) Colorless liquid in appearance. The molecular weight is 336 . The specific gravity is 1.104 ( 20 ℃ ). The flash point is 199℃ . Boiling point is 345℃ ( 760mmHg). The freezing point is below -20℃ . The viscosity is 51cp (25°C). FDA qualified product (coating, adhesive).
( 2 ) It acts as a plasticizer for natural rubber, synthetic rubber, natural resin, and synthetic resin. It can give a compounding agent that is odorless, tasteless, light resistance, alkali resistance, cold resistance, and elasticity. It can also be used as a plasticizer for polyvinyl chloride resin food and medical products, and polystyrene or natural resin.
9.2 tetrahydrophthalic acid derivatives ( Tatrahydrophthalicacid derivalives )
9.2.1 tetrahydro phthalate -2- ethyl ester ( DI-2-ethylhexyl tetrahydrophthalate )
( 1 ) Character liquid. The molecular weight is 395 . The specific gravity is 0.969 ( 20 ℃ ). The flash point is 202℃ . The viscosity is 47.2cp (25°C). Color (APHA ) 30.
( 2 ) It acts as a plasticizer for cycloaliphatic dibasic acid ester. Cold resistance and sol viscosity stability are better than other phthalates. Moreover, the plasticizer itself has low viscosity and is easy to handle. Used in artificial leather, film, paste, hose, hard tube.
9.3 adipic acid derivatives ( Adipic acid derivalives )
9.3.1 Dibutyl adipate (DBA )
( 1 ) Character liquid. The molecular weight is 258 . The specific gravity is 0.96 ~ 0.965 ( 20 ℃ ). The flash point is 150 ～160 ℃ . Viscosity 5-6cp (25°C).
( 2 ) It acts as a plasticizer for synthetic rubber, vinyl resin and cellulose resin. Excellent cold resistance, but not very good durability, low viscosity and high volatility. Therefore, the amount of polyvinyl chloride resin is limited, but the solubilization performance is excellent. Used in nitrocellulose paint.
9.3.2 Dimethyl adipate ( dimethyl adipate; DMA )
( 1 ) Transparent liquid in appearance. The molecular weight is 174.2 . The specific gravity is 1.064 ( 20 ℃ ). The flash point is 123℃