CN110499032B - Self-lubricating addition type liquid silicone rubber and preparation method and application thereof - Google Patents
Self-lubricating addition type liquid silicone rubber and preparation method and application thereof Download PDFInfo
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- CN110499032B CN110499032B CN201910800917.2A CN201910800917A CN110499032B CN 110499032 B CN110499032 B CN 110499032B CN 201910800917 A CN201910800917 A CN 201910800917A CN 110499032 B CN110499032 B CN 110499032B
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The invention relates to a self-lubricating addition type liquid silicone rubber which comprises the following raw materials in parts by weight: 120-200 parts of an alkenyl-containing polysiloxane; 1-15 parts of hydrogenated polysiloxane; 30-80 parts of fumed silica; 10-30 parts of silazane white carbon black treating agent; 1-30 parts of methyl phenyl silicone oil; 0.004-0.06 part of Si-H addition catalyst; 0.03-0.6 parts of inhibitor. According to the invention, the types and the amounts of the alkenyl-containing polysiloxane and the hydrogenated polysiloxane in the base rubber, the component A and the component B are screened, and the oil penetration rate and the product performance are controlled through raw material screening and formula design, so that the addition type liquid silicone rubber with high tear strength (more than or equal to 45kN/m) and low permanent compression deformation rate (less than or equal to 20%) is provided, and meanwhile, the oil penetration is stable, and the long-term self-lubricating effect can be kept. The self-lubricating addition type liquid silicone rubber provided by the invention is simple in preparation method, low in cost and easy to obtain raw materials, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of silicone rubber, in particular to addition type liquid silicone rubber.
Background art:
the liquid silicone rubber has good high and low temperature resistance, small performance change in a wide temperature range, ozone resistance, weather resistance, electrical insulation, flame retardant property and other excellent performances, and meanwhile, the process has high automation degree, high production efficiency, environmental protection, no by-product and continuously expanded application field. However, liquid silicone rubber has a characteristic of large friction coefficient and poor wear resistance, which limits its application in some fields requiring low friction.
After the self-lubricating silicone rubber material is cured and formed, a plurality of fine oil droplets can be slowly separated out from the surface of the product. Therefore, the surface friction can be effectively reduced, the lubricating effect is achieved, and the damage to a workpiece can be reduced or avoided. The self-lubricating silicone rubber can be widely applied to the fields of electronics, automobiles, medical treatment and the like, such as cable harness sealing, plug-in and pull-out pieces, O-shaped rings, sealing gaskets, medical diaphragms and the like. The self-lubricating liquid silicone rubber has the advantages of continuous and controllable oil production, good mechanical property and low compression deformation, thereby ensuring the requirements of sealing and service life of the product.
Chinese patent CN104910633A discloses a preparation method of self-oil-permeable solid silicone rubber. Chinese patent CN104479365B discloses a preparation method of self-bleeding solid silicone rubber, wherein no important index compression set is mentioned. Chinese patent CN106221240 discloses a self-lubricating silicone rubber and a preparation method thereof, and the prepared silicone rubber has low tear strength (less than or equal to 20KN/m) and complex preparation process and cannot meet the actual requirements. There are some drawbacks in the above patents: firstly, a higher proportion of phenyl silicone oil needs to be added to obtain a better self-lubricating effect. Although the phenyl silicone oil can achieve certain oil seepage and oil outlet effects, the oil outlet effect is poor after a long time, the oil can not be continuously discharged, and the service life of the silicone rubber is shortened; secondly, the solid silicone rubber base material has high viscosity, has poor compatibility with the oil-penetrating agent phenyl silicone oil with lower viscosity, is easy to stick a stick on an open mill, has complex processing technology and has certain danger; thirdly, if the platinum catalyst is used alone, the compression permanent deformation rate of the self-oil-permeable solid silica gel is as high as 42 percent; by adopting a platinum bisulphide-peroxide vulcanization system, after secondary vulcanization, the compression deformation rate is reduced to 20%, but the peroxide vulcanization agent has peculiar smell and is not environment-friendly enough. Therefore, the development of a self-lubricating addition type liquid silicone rubber with low compression set rate and high tear strength is needed.
Disclosure of Invention
In view of the above, the invention aims to provide a self-lubricating liquid silicone rubber, which mainly solves three core problems through raw material and formula design: 1. the tearing strength is high (more than or equal to 45KN/m), and the tearing resistance requirement of installation and use is met; 2. the platinum vulcanized liquid rubber has ultralow compression permanent deformation (secondary vulcanization is not needed, and the compression permanent deformation rate of primary vulcanization is lower than 20 percent), improves the sealing property of the material, and meets the requirement of the stability of a terminal product; 3. long-term controllable lubricity, and the requirements of self-lubrication and long service life are met.
A self-lubricating addition type liquid silicone rubber comprises the following raw materials in parts by weight: 120-200 parts of an alkenyl-containing polysiloxane; 1-15 parts of hydrogenated polysiloxane; 30-80 parts of fumed silica; 10-30 parts of silazane white carbon black treating agent; 1-30 parts of methyl phenyl silicone oil; 0.004-0.06 part of Si-H addition catalyst; 0.03-0.6 parts of inhibitor.
Preferably, the self-lubricating addition type liquid silicone rubber is a two-component silicone rubber comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 100 portions of base adhesive 130 portions, 0 to 30 portions of alkenyl-containing polysiloxane, 0 to 15 portions of methyl phenyl silicone oil, 0.005 to 0.06 portion of Si-H addition catalyst; the component B comprises the following raw materials in parts by weight: 100 portions of base adhesive 130 portions, 0 to 30 portions of alkenyl-containing polysiloxane, 0 to 15 portions of methyl phenyl silicone oil, 0.03 to 0.6 portion of inhibitor and 1 to 15 portions of hydrogenated polysiloxane; the 100-130 parts of base adhesive is prepared from 60-80 parts of alkenyl-containing polysiloxane, 15-40 parts of fumed silica and 5-15 parts of silazane white carbon black treating agent;
the condition is that the total dosage of the component A and the component B is 1 to 30 parts.
Further preferably, the self-lubricating addition type liquid silicone rubber is a two-component silicone rubber comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 100 portions of base adhesive 130 portions, 5 to 20 portions of alkenyl-containing polysiloxane, 1 to 5 portions of methyl phenyl silicone oil, 0.005 to 0.02 portion of Si-H addition catalyst; the component B comprises the following raw materials in parts by weight: 100 portions of base adhesive 130 portions, 5 to 20 portions of alkenyl-containing polysiloxane, 1 to 5 portions of methyl phenyl silicone oil, 0.05 to 0.4 portion of inhibitor and 4 to 10 portions of hydrogenated polysiloxane; the base adhesive is prepared from 60-80 parts of alkenyl-containing polysiloxane, 20-30 parts of fumed silica and 5-15 parts of silazane white carbon black treating agent.
As is well known to those skilled in the art, when both an alkenyl polysiloxane and a hydrido polysiloxane are present in the composition, an amount of inhibitor is added to inhibit the Si-H addition reaction.
In the invention, the alkenyl-containing polysiloxane is polysiloxane containing alkenyl with carbon-carbon double bonds, the alkenyl is at least one of vinyl, propenyl and butenyl, the alkenyl is on the terminal group and/or side chain of the polysiloxane, and the content of the alkenyl is 0.02-1 mmol/g; the hydrogenated polysiloxane is polysiloxane containing active hydrogen at the end group and/or side chain, wherein the active hydrogen mass content is 2-16 mmol/g;
preferably, the alkenyl-containing polysiloxane in the component A and/or the component B has an alkenyl content of 0.03-0.9 mmol/g; the active hydrogen mass content of the hydrogenated polysiloxane is 2-12 mmol/g.
Further preferably, the viscosity of the terminal alkenyl-containing alkenylpolysiloxane of component A and component B is 3500-30000 mPa.s, the alkenyl content is 0.02-0.25mmol/g, more preferably the viscosity is 10000-30000 mPa.s, the alkenyl content is 0.03-0.1 mmol/g; the viscosity of the alkenylpolysiloxane having alkenyl groups in the side chains is 1000-5000 mPas, the alkenyl content is 0.1-0.3mmol/g, and more preferably the viscosity is 1000-2000 mPas, the alkenyl content is 0.1-0.2 mmol/g; the viscosity of the alkenyl polysiloxane containing alkenyl groups at both the terminal group and the side chain is 300-1000 mPas, the alkenyl content is 0.6-1mmol/g, and the viscosity is more preferably 400-700 mPas, the alkenyl content is 0.7-0.9 mmol/g;
and/or the active hydrogen content of the end group hydrogenpolysiloxane is 2-5mmol/g, the active hydrogen content of the side chain hydrogenpolysiloxane is 2.5-15mmol/g, and the active hydrogen content of both the end group hydrogenpolysiloxane and the side chain hydrogenpolysiloxane is 3-15 mmol/g.
More preferably, the alkenyl polysiloxane comprises a polysiloxane having an alkenyl group in a side chain, that is, the alkenyl polysiloxane comprises one or a combination of two of a side chain alkenyl polysiloxane and a polysiloxane having an alkenyl group in both a terminal group and a side chain, provided that the side chain alkenyl polysiloxane and the polysiloxane having an alkenyl group in both a terminal group and a side chain in the a component and the B component are used in a total amount of 2 to 20 parts, preferably 10 to 20 parts.
In the invention, the preparation method of the base rubber comprises the following steps: 40-45 parts of end group containing alkenyl polysiloxane with the viscosity of 60000 mPas-1000000 mPas and the alkenyl content of 0.02-0.035mmol/g, 2-5 parts of side chain containing alkenyl polysiloxane with the viscosity of 100000 mPas-250000 mPas and the alkenyl content of 0.6-1.0mmol/g, 15-40 parts of gas phase white carbon black and 5-15 parts of silazane are uniformly mixed in water, fully mixed for 1-2 hours under the protection of inert atmosphere below 60-90 ℃, vacuumized for 2-4 hours after the temperature is raised to 130-180 ℃, kept at 130-180 ℃ during vacuumization, then cooled to 120-140 ℃, and then diluted and uniformly stirred by adding 15-20 parts of end group containing alkenyl polysiloxane with the viscosity of 20000 mPas-60000 mPas and the alkenyl content of 0.03-0.07mmol/g, thus obtaining the base rubber.
The methyl phenyl silicone oil is selected from one or more of methyl phenyl polysiloxane with two ends capped by diphenyl, methyl phenyl polysiloxane with two ends capped by monophenyl and methyl phenyl polysiloxane with two ends capped by methyl, preferably methyl phenyl polysiloxane with two ends capped by diphenyl; the methyl phenyl silicone oil is a mixture of one or more methyl phenyl silicone oils with different refractive indexes, and the viscosity of the methyl phenyl silicone oil ranges from 50 to 500mpa & s, preferably 100-300mpa & s.
The inhibitor is not particularly limited, and is a reagent which can inhibit the addition of Si-H in the art, and is generally an alkynol, and examples thereof include, but are not limited to, at least one of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-ol, and 3, 5-dimethyl-1-hexyn-3-ol, and 3-methyl-1-dodecyn-3-ol.
The Si-H addition catalyst is transition metal oxide and complex thereof such as a Kaster type, carbene type, supported type and the like, and a Kaster type platinum catalyst is preferred.
The white carbon black is gas-phase white carbon black subjected to in-situ grafting treatment by silazane and other treating agents, and the specific surface area of the white carbon black is not less than 200m2Per g, preferably 250-400m2(ii)/g; the white carbon black treating agent is at least one of hexamethyl silazane, tetramethyl divinyl silazane, heptamethyl disilazane, vinyl double-end socket and hydroxyl silicone oil.
The invention also provides a preparation method of the self-lubricating addition type liquid silicone rubber, which comprises the following steps:
(1) preparing base glue by using 60-80 parts of alkenyl-containing polysiloxane, 15-40 parts of fumed silica and 5-15 parts of silazane white carbon black treating agent under the vacuum condition of 130-180 ℃;
(2) preparation of the component A: 100 portions of base rubber 130, 0 to 30 portions of alkenyl-containing polysiloxane, 0 to 15 portions of methyl phenyl silicone oil and 0.005 to 0.06 portion of Si-H addition catalyst are mixed and dispersed evenly, and then vacuumized and defoamed to obtain a self-lubricating liquid silicone rubber A component;
(3) the component B is prepared by uniformly mixing and dispersing 100-130 parts of base rubber, 0-30 parts of alkenyl-containing polysiloxane, 0-15 parts of methyl phenyl silicone oil, 0.03-0.6 part of inhibitor and 1-15 parts of hydrogenated polysiloxane, and then vacuumizing and defoaming to obtain the self-lubricating liquid silicone rubber component B;
the condition is that the total dosage of the methyl phenyl silicone oil in the component A and the component B is 1 to 30 parts.
Preferably, the preparation method of the self-lubricating addition type liquid silicone rubber comprises the following steps:
(1) preparing base glue by using 60-80 parts of alkenyl-containing polysiloxane, 20-30 parts of fumed silica and 5-15 parts of silazane white carbon black treating agent under the vacuum condition of 130-180 ℃;
(2) preparation of the component A: 100 portions of base rubber 130, 5 portions to 20 portions of alkenyl-containing polysiloxane, 1 portion to 5 portions of methyl phenyl silicone oil and 0.005 portion to 0.02 portion of Si-H addition catalyst are mixed and dispersed evenly, and then vacuumized and defoamed to obtain a self-lubricating liquid silicone rubber A component;
(3) the component B is prepared by uniformly mixing and dispersing 100-130 parts of base rubber, 5-20 parts of alkenyl-containing polysiloxane, 1-5 parts of methyl phenyl silicone oil, 0.03-0.4 part of inhibitor and 4-10 parts of hydrogenated polysiloxane, and then vacuumizing and defoaming to obtain the self-lubricating liquid silicone rubber component B;
it is well known to those skilled in the art that when the components contain an alkenyl polysiloxane and a hydro polysiloxane, an inhibitor should also be added to the components to inhibit the reaction between the two.
The invention also provides application of the self-lubricating addition type liquid silicone rubber, and the self-lubricating addition type liquid silicone rubber is used in the fields of electronics, automobiles and medical application. The tear strength of the self-lubricating addition type liquid silicone rubber is more than or equal to 45KN/m, and the one-time vulcanization compression permanent deformation rate is lower than 20%.
The process conditions such as temperature and time are preferred ranges, but the scope of the present invention is not limited thereto.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the components and structures of alkenyl-containing polysiloxane and hydrogenated polysiloxane in the liquid silicone rubber bi-component, such as the proportion of raw materials and the contents of alkenyl and active hydrogen, are specially selected, and the liquid silicone rubber which has high tearing strength and ultralow primary platinum vulcanization compression set is obtained by matching with other raw materials.
Secondly, self-lubricating liquid silicone rubber with high tearing strength is obtained, and the tearing strength of the product is higher than 42KN-1Far higher than the current patent report 15-30KN.m-1。
Thirdly, the one-time vulcanization compression set rate of the obtained self-lubricating product is lower than 20 percent, and domestic reports are not found.
And fourthly, controlling the oil penetration rate and long-term lubrication of the product by regulating and controlling the crosslinking density of the product, the type of the phenyl silicone oil and the addition amount of the phenyl silicone oil.
Detailed Description
The self-lubricating addition type liquid silicone rubber of the present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The term "parts" as used in the detailed description means parts by weight unless otherwise specified.
Preparation examplePreparation of the base rubber
Preparation example 1
42 parts by weight of a terminal vinylpolysiloxane having a viscosity of 60000 mPas and an alkenyl group content of 0.03mmol/g, 2.8 parts of a side-chain vinylpolysiloxane having a viscosity of 200000 mPas and an alkenyl group content of 0.8mmol/g, 25 parts of a side-chain vinylpolysiloxane having a BET specific surface area of 300m2The preparation method comprises the following steps of fully mixing 7.05 parts of hexamethyldisilazane, 0.15 part of tetramethyldivinylsilazane and 6.5 parts of deionized water in a piece of fumed silica/g for 1-2 hours under the protection of inert atmosphere below 80 ℃, heating to 130-150 ℃, vacuumizing for 2-4 hours, and keeping the temperature during vacuumizingAnd cooling to 110-140 ℃ at 150-170 ℃, adding 16.5 parts of alkenyl polysiloxane with viscosity of 20000 mPas and vinyl content of 0.035mmol/g, and uniformly stirring to obtain the liquid silicone rubber base rubber 1.
Preparation example 2
In a kneader or planetary mixer 40 parts by weight of a methylvinylpolysiloxane having a viscosity of 60000 mPas and a content of alkenyl groups of 0.03mmol/g, 3 parts of a polyvinylpolysiloxane having a viscosity of 250000 mPas and a content of alkenyl groups of 0.9mmol/g, 27.5 parts of a polyvinylpolysiloxane having a BET specific surface area of 400m2The preparation method comprises the following steps of fully mixing 8 parts of fumed silica, 8 parts of hexamethyldisilazane, 0.5 part of tetramethyldivinylsilazane and 4.5 parts of deionized water at the temperature of below 80 ℃ for 1-2 hours under the protection of an inert atmosphere, heating to 130-150 ℃, vacuumizing for 2-4 hours, keeping the temperature at 150-170 ℃ during vacuumizing, cooling to 110-140 ℃, adding 17 parts of methyl vinyl polysiloxane with the viscosity of 60000 mPa-s and the alkenyl content of 0.030mmol/g, and uniformly stirring to obtain the liquid silicone rubber base adhesive 2.
Comparative preparation example 1
In a kneader or planetary mixer, 60 parts by weight of a terminal vinylpolysiloxane having a viscosity of 60000 mPas and a vinyl content of 0.035mmol/g and a BET specific surface area of 300m2And mixing 7.05 parts of hexamethyldisilazane, 0.15 part of tetramethyldivinylsilazane and 6.5 parts of deionized water in a ratio of one gram to another gram in an inert atmosphere at a temperature of below 80 ℃ for 1-2 hours, heating to 130-150 ℃, vacuumizing, keeping the temperature at 150-170 ℃ during vacuumizing, cooling to 110-140 ℃, and uniformly stirring to obtain the liquid silicone rubber base adhesive 3.
ExamplesPreparation of liquid silicone rubber
Example 1
Preparing an AB component: stirring and dispersing 100 parts of base rubber 1, 4.1 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 7.2 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 3.0 parts of polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, 0.014 part of Karster catalyst and 2.3 parts of methyl phenyl silicone oil with the viscosity of 300 mPas in a planetary stirrer for 30-40min, uniformly mixing, vacuumizing and defoaming to obtain the self-lubricating low-pressure rheological fluid silicone rubber A component. And stirring and dispersing 100 parts of base rubber 1, 8.8 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 3.5 parts of polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, both a terminal group and a side chain containing vinyl, 2.3 parts of a methyl phenyl silicone oil mixture with the viscosity of 200 mPas, 5.1 parts of hydrogenated polysiloxane with the hydrogen content of 7mmol/g and the side chain containing Si-H, and 0.08 part of 3-methyl-1-dodecyne-3-ol in a planetary stirrer for 30-40min, uniformly mixing, vacuumizing and defoaming to obtain the self-lubricating low-pressure silicone fluid rubber component B.
Examples 1 to 1
A liquid silicone rubber was prepared in the same manner as in example 1, except that in the preparation of component A, the viscosity was 1000 mPas, and the amount of the side-chain vinylpolysiloxane having an alkenyl group content of 0.12mmol/g was 15 parts.
Examples 1 to 2
A liquid silicone rubber was prepared in the same manner as in example 1, except that in the preparation of component A, the viscosity was 1000 mPas, and the amount of the side-chain vinylpolysiloxane having an alkenyl group content of 0.12mmol/g was 2 parts.
Example 2
Preparing an AB component: and stirring and dispersing 120 parts of base rubber 2, 6.1 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 5.2 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 3.5 parts of methyl phenyl silicone oil mixture with the viscosity of 100 mPas and 0.015 part of Kaster catalyst in a planetary stirrer for 30-40min, uniformly mixing, vacuumizing and defoaming to obtain the self-lubricating low-pressure rheological fluid silicone rubber A component. And stirring and dispersing 120 parts of base rubber 1, 5.5 parts of end group and side chain containing vinyl polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, 2.3 parts of hydrogenated polysiloxane with the hydrogen content of 7mmol/g and the side chain containing Si-H, 0.9 part of hydrogenated polysiloxane with the hydrogen content of 13mmol/g, 3 parts of methyl phenyl silicone oil mixture with the viscosity of 100 mPas and 0.09 part of 1-ethynyl-1-cyclohexanol in a planetary stirrer for 30-40min, uniformly mixing, vacuumizing and defoaming to obtain the self-lubricating low-pressure rheological fluid silicone rubber B component.
Example 3
Preparing an AB component: stirring and dispersing 100 parts of base rubber 1, 9.2 parts of terminal vinyl polysiloxane with the viscosity of 24000 mPas and the alkenyl content of 0.042mmol/g, 2.1 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 1.2 parts of side chain vinyl polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, 0.014 part of Karster catalyst and 2.3 parts of methyl phenyl silicone oil with the viscosity of 300 mPas in a planetary stirrer for 30-40min, uniformly mixing, vacuumizing and defoaming to obtain the self-lubricating low-pressure silicone fluid rubber A component. And stirring and dispersing 100 parts of base rubber 1, 2.1 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 5.5 parts of end group and side chain both containing vinyl polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, 2.3 parts of methyl phenyl silicone oil mixture with the viscosity of 200 mPas, 4.5 parts of hydrogenated polysiloxane with the hydrogen content of 10mmol/g and the side chain both containing Si-H, and 0.08 part of 3-methyl-1-dodecyn-3-ol in a planetary stirrer for 30-40min, uniformly mixing, vacuumizing and defoaming to obtain the self-lubricating low-pressure silicone fluid rubber component B.
Example 4
Preparing an AB component: 100 parts of base rubber 1, 4.7 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 2.6 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 1.2 parts of polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, wherein both the terminal group and the side chain contain vinyl, 0.014 part of Kanster catalyst, 0.08 part of 3-methyl-1-dodecyn-3-ol and 2.3 parts of methyl phenyl silicone oil with the viscosity of 300 mPas are stirred and dispersed in a planetary stirrer for 30-40min, and the self-lubricating low-pressure rheological fluid silicone rubber A component is obtained after uniform mixing, vacuum degassing. And stirring and dispersing 100 parts of base rubber 1, 5.3 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 4.8 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 5.5 parts of polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, wherein both the terminal and the side chain contain vinyl, 2.3 parts of a methyl phenyl silicone oil mixture with the viscosity of 200 mPas, 2.5 parts of hydrogenated polysiloxane with the hydrogen content of 7mmol/g and the side chain containing Si-H, 3.1 parts of hydrogenated polysiloxane with the hydrogen content of 10mmol/g, wherein both the terminal and the side chain contain Si-H in a planetary stirrer for 30-40min, uniformly mixing, vacuumizing and defoaming to obtain the self-lubricating low-pressure rheological fluid silicone rubber B component.
Example 5
Preparing an AB component: 100 parts of base rubber 1, 5 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 3.6 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 3.3 parts of polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, 0.018 parts of Kaster catalyst, 0.06 part of 3-methyl-1-dodecyne-3-ol and 2.3 parts of methyl phenyl silicone oil with the viscosity of 300 mPas are mixed, stirred and dispersed in a planetary stirrer for 30-40min, uniformly mixed and vacuumized and defoamed to obtain the self-lubricating low-pressure silicone fluid rubber A component. 100 parts of base rubber 1, 5 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 3.6 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 3.3 parts of polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, wherein both the terminal group and the side chain contain vinyl, 4.5 parts of hydrogenated polysiloxane with the hydrogen content of 10mmol/g, both the terminal group and the side chain contain Si-H, 0.06 part of 3-methyl-1-dodecyn-3-ol and 2.3 parts of methyl phenyl silicone oil with the viscosity of 300 mPas are mixed, stirred and dispersed in a planetary stirrer for 30-40min, uniformly mixed and vacuumized and defoamed to obtain the self-lubricating low-pressure rheological fluid silicone rubber B component.
Example 6
Preparing an AB component: 100 parts of base rubber 2, 4.7 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 4.2 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 2.4 parts of polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, wherein both the terminal group and the side chain contain vinyl, 0.018 parts of Kanster catalyst, 0.06 parts of 3-methyl-1-dodecyn-3-ol and 2.3 parts of methyl phenyl silicone oil with the viscosity of 300 mPas are mixed, stirred and dispersed in a planetary stirrer for 30-40min, and the self-lubricating low-pressure rheological fluid silicone rubber A component is obtained after uniform mixing, vacuumizing and defoaming. 100 parts of base rubber 2, 5.1 parts of terminal vinyl polysiloxane with the viscosity of 20000 mPas and the alkenyl content of 0.035mmol/g, 2.3 parts of side chain vinyl polysiloxane with the viscosity of 1000 mPas and the alkenyl content of 0.12mmol/g, 4.7 parts of polysiloxane with the viscosity of 400 mPas and the alkenyl content of 0.9mmol/g, wherein both the terminal group and the side chain contain vinyl, 4.5 parts of hydrogenated polysiloxane with the hydrogen content of 10mmol/g, both the terminal group and the side chain contain Si-H, 0.06 part of 3-methyl-1-dodecyne-3-ol and 2.3 parts of methyl phenyl silicone oil with the viscosity of 300 mPas are mixed, stirred and dispersed in a planetary stirrer for 30-40min, mixed uniformly and vacuumized to obtain the self-lubricating low pressure rheological fluid silicone rubber component B.
Comparative example 1
The other procedure was the same as in example 1 except that the base rubber 3 of comparative preparation example 1 was used.
Comparative example 2
The other procedure is the same as in example 1, except that in the preparation of the A-and B-components, no side-chain vinylpolysiloxane is added.
Application example
The detection method of the compression permanent deformation adopts GB/T7759; the tensile strength and elongation at break were measured using ASTM D412; the hardness is detected by ASTM D2240; the tear strength was measured using ASTM D624; the detection method of the rebound resilience adopts ASTM D7121; the oil seepage rate detection method is used for testing the mass precipitation amount of the phenyl silicone oil.
The test samples of tensile strength, elongation at break, hardness, tear strength, rebound resilience and oil evolution rate are prepared by mixing the component A and the component B in the example according to the proportion of 1:1, and curing at 170 ℃ for 5min to obtain a 2mm test piece. The compression set DRC is calculated according to the national standard and is made into the product with the diameter of 29.5mm and the height h0(about 12.5 mm) and then height h of a suitable stopper2Compressing the test block by 25%, aging in an oven at 180 deg.C for 22h, and cooling at 25 deg.C and 50% humidity for half an hour to test the thickness h of the test block1According to the formula DRC ═ h0-h1)/(h0-h2)*100％。
The product properties of inventive examples 1-7 and comparative example 1 were compared and the results are shown in table 1.
TABLE 1
Table 1 is a comparison of the properties of the liquid silicone rubber silicone sheets obtained in the examples and comparative examples. As can be seen from Table 1, the liquid silicone rubber provided by the invention has excellent comprehensive properties, and particularly has very high tear strength (not less than 45kN/m) and low permanent compression set (not more than 20%). The liquid silicone rubber provided by the invention has good self-lubricating property and stable oil seepage amount, and the oil seepage amount of 30 days can also meet the actual requirement.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily make various changes or modifications according to the main concept and spirit of the present invention, so the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. The self-lubricating addition type liquid silicone rubber is characterized by being two-component and comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 100 portions of base adhesive 130 portions, 5 to 20 portions of alkenyl-containing polysiloxane, 1 to 5 portions of methyl phenyl silicone oil, 0.005 to 0.02 portion of Si-H addition catalyst; the component B comprises the following raw materials in parts by weight: 100 portions of base adhesive 130 portions, 5 to 20 portions of alkenyl-containing polysiloxane, 1 to 5 portions of methyl phenyl silicone oil, 0.05 to 0.4 portion of inhibitor and 4 to 10 portions of hydrogenated polysiloxane;
the preparation method of the base rubber comprises the following steps: 40-45 parts of terminal group containing alkenyl polysiloxane with the viscosity of 60000 mPa.s-1000000 mPa.s and the alkenyl content of 0.02-0.035mmol/g, 2-5 parts of side chain containing alkenyl polysiloxane with the viscosity of 200000 mPa.s-250000 mPa.s and the alkenyl content of 0.6-1.0mmol/g, 15-40 parts of gas phase white carbon black and 5-15 parts of silazane are uniformly mixed in water, fully mixed for 1-2 hours under the protection of inert atmosphere below 60-90 ℃, vacuumized for 2-4 hours after the temperature is raised to 130-180 ℃, kept at 130-180 ℃ during vacuumization, then cooled to 120-140 ℃, and then diluted by adding 15-20 parts of terminal group containing alkenyl polysiloxane with the viscosity of 20000mPa mPa.s-60000 mPa.s and the alkenyl content of 0.03-0.07mmol/g, stirring uniformly to obtain base rubber;
the alkenyl-containing polysiloxane is polysiloxane containing alkenyl with carbon-carbon double bond, the alkenyl is at least one of vinyl, propenyl and butenyl, the alkenyl is on the terminal group and/or side chain of the polysiloxane, and the hydrogenated polysiloxane refers to polysiloxane containing active hydrogen on the terminal group and/or side chain; the viscosity of the alkenyl polysiloxane with the terminal group containing alkenyl in the component A and the component B is 10000-30000 mPa.s, and the alkenyl content is 0.03-0.1 mmol/g; the viscosity of the alkenyl polysiloxane containing alkenyl at the side chain is 1000-2000 mPa.s, and the content of the alkenyl is 0.1-0.2 mmol/g; the viscosity of the alkenyl polysiloxane containing alkenyl at both the end group and the side chain is 400-700 mPa.s, and the content of the alkenyl is 0.7-0.9 mmol/g;
the active hydrogen content of the end group hydrogenous polysiloxane is 2-5mmol/g, the active hydrogen content of the side chain hydrogenous polysiloxane is 2.5-15mmol/g, and the active hydrogen content of both the end group hydrogenous polysiloxane and the side chain hydrogenous polysiloxane is 3-15 mmol/g;
the alkenyl-containing polysiloxane comprises polysiloxane with necessarily containing alkenyl on a side chain, namely the alkenyl polysiloxane comprises the combination of side chain alkenyl polysiloxane and one or two of polysiloxane with alkenyl on both a terminal group and a side chain, wherein the total using amount of the side chain alkenyl-containing polysiloxane and the polysiloxane with alkenyl on both the terminal group and the side chain in the component A and the component B is 10-20 parts;
the viscosity range of the methyl phenyl silicone oil is 50-500mpa · s.
2. The liquid silicone rubber according to claim 1, wherein the methylphenyl silicone oil is selected from one or more of methylphenyl polysiloxane terminated with bisphenyl groups at both ends, methylphenyl polysiloxane terminated with monophenyl groups at both ends, and methylphenyl polysiloxane terminated with methyl groups at both ends; and/or
The inhibitor is selected from at least one of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-ol, 3, 5-dimethyl-1-hexyn-3-ol and 3-methyl-1-dodecyn-3-ol; and/or
The Si-H addition catalyst is selected from at least one of a Karster type, a carbene type and a supported type; and/or
The white carbon black is fumed silica subjected to in-situ grafting treatment by a treating agent, and the specific surface area of the fumed silica is not less than 200m2(ii)/g; the white carbon black treating agent is at least one of hexamethyl silazane, tetramethyl divinyl silazane, heptamethyl disilazane, vinyl double-end socket and hydroxyl silicone oil.
3. The liquid silicone rubber according to claim 2, wherein the silica white specific surface area is 250-400m2/g。
4. The liquid silicone rubber according to claim 2, wherein the viscosity of the methylphenyl silicone oil is 100-300 mpa-s.
5. A method for producing the liquid silicone rubber described in any one of claims 1 to 4, comprising the steps of:
(1) the preparation method of the base rubber comprises the following steps: 40-45 parts of terminal group containing alkenyl polysiloxane with the viscosity of 60000 mPa.s-1000000 mPa.s and the alkenyl content of 0.02-0.035mmol/g, 2-5 parts of side chain containing alkenyl polysiloxane with the viscosity of 200000 mPa.s-250000 mPa.s and the alkenyl content of 0.6-1.0mmol/g, 15-40 parts of gas phase white carbon black and 5-15 parts of silazane are uniformly mixed in water, fully mixed for 1-2 hours under the protection of inert atmosphere below 60-90 ℃, vacuumized for 2-4 hours after the temperature is raised to 130-180 ℃, kept at 130-180 ℃ during vacuumization, then cooled to 120-140 ℃, and then diluted by adding 15-20 parts of terminal group containing alkenyl polysiloxane with the viscosity of 20000mPa mPa.s-60000 mPa.s and the alkenyl content of 0.03-0.07mmol/g, stirring uniformly to obtain base rubber;
(2) preparation of the component A: 100 portions of base rubber 130, 5 portions to 20 portions of alkenyl-containing polysiloxane, 1 portion to 5 portions of methyl phenyl silicone oil and 0.005 portion to 0.02 portion of Si-H addition catalyst are mixed and dispersed evenly, and then vacuumized and defoamed to obtain a self-lubricating liquid silicone rubber A component;
(3) the component B is prepared by uniformly mixing and dispersing 100-130 parts of base rubber, 5-20 parts of alkenyl-containing polysiloxane, 1-5 parts of methyl phenyl silicone oil, 0.05-0.4 part of inhibitor and 4-10 parts of hydrogenated polysiloxane, and then vacuumizing and defoaming to obtain the self-lubricating liquid silicone rubber component B.
6. Use of the self-lubricating addition type liquid silicone rubber according to any one of claims 1 to 4, characterized by being used in the electronic, automotive field.
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| CN111231473B (en) * | 2020-01-17 | 2021-12-07 | 江西赛欧特科新材料有限公司 | Synthetic leather of organic silicon composite polyurethane and preparation method thereof |
| CN111171579B (en) * | 2020-02-25 | 2022-06-14 | 江西蓝星星火有机硅有限公司 | Wear-resistant temperature-resistant self-lubricating silicone rubber and preparation method and application thereof |
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| CN112852167B (en) * | 2021-01-12 | 2023-04-28 | 江西蓝星星火有机硅有限公司 | Low-hardness transparent liquid silicone rubber composition with low compression deformation, and preparation method and application thereof |
| CN114790335B (en) * | 2022-06-02 | 2023-06-30 | 埃肯有机硅(广东)有限公司 | Heat-resistant addition type liquid silicone rubber composition |
| WO2023243706A1 (en) * | 2022-06-17 | 2023-12-21 | 積水化学工業株式会社 | Silicone composition, heat dissipating member, and electronic apparatus |
| CN115612446B (en) * | 2022-10-27 | 2024-01-26 | 江西蓝星星火有机硅有限公司 | Heat-conducting addition type organic silicon composition for encapsulation |
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