CN1195019C - Isocyanate cross-linked high-temp, vulcanized silicone rubber and its preparation method - Google Patents
Isocyanate cross-linked high-temp, vulcanized silicone rubber and its preparation method Download PDFInfo
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- CN1195019C CN1195019C CNB031124674A CN03112467A CN1195019C CN 1195019 C CN1195019 C CN 1195019C CN B031124674 A CNB031124674 A CN B031124674A CN 03112467 A CN03112467 A CN 03112467A CN 1195019 C CN1195019 C CN 1195019C
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Abstract
The present invention relates to isocyanate cross-linked high-temperature vulcanized silicone rubber and a preparation method thereof, which belongs to the technical field of rubber materials. The high-temperature vulcanized silicone rubber comprises raw material components of 100 portions of aminoalkyl polysiloxane raw rubber (whose molecular weight is from 300000 to 400000), 30 to 65 portions of reinforcing filler and 0.2 to 4.0 portions of closed isocyanate. In the preparation method, an open type dual-roller rubber mixing machine is used for processing, and the temperature of rollers is room temperature; the aminoalkyl polysiloxane raw rubber is firstly added onto the rollers, and white carbon black is added after the rollers are coated by the aminoalkyl polysiloxane raw rubber for the mixing time of 25 to 60 minutes. After the rubber material is tightly rolled, the cross-linked agent of closed isocyanate is added, and then the thin rubber material is rolled into sheets which are primarily vulcanized on a vulcanizing press and then are secondarily vulcanized in a baking oven with a blast fan. The silicone rubber of the isocyanate cross-linked system of the present invention has the advantage of favorable combination property and reaches application requirements for ordinary silicone rubber; therefore, the silicone rubber can be used for processing various silicone rubber products.
Description
(1) technical field
The present invention relates to a kind of new type high temperature sulphurated siliastic and preparation method thereof, belong to the elastomeric material technical field.
(2) background technology
Silicon rubber has excellent high-low temperature resistant, weather-proof, anti-ozone, anti-electric-arc, electric insulating quality, highly air-permeable and physiology inertia etc., and silastic product has excellent comprehensive performance and good technology economic, so obtained to use widely in industry such as aviation, aerospace, electric, electronics, electrical equipment, chemical industry, instrument, automobile, machinery and health care, daily life every field.Referring to the loose people of good fortune, Wang Yilu, " organosilicon synthesis technique and product application ", Chemical Industry Press, Beijing, 1999, P604-609.Silicon rubber mainly is divided into high temperature vulcanized and self cure two big classes by vulcanization, also has radiation crosslinking and photo-crosslinking dual mode in addition.Room temperature vulcanized silicone rubber divides one-pack type (as dealcoholizing-type, decarboxylation acid type, take off seven kinds on amine type etc.) and two-component-type (comprising three kinds of dehydration-types, dealcoholizing-type, depickling type), and the basic glue of use mainly is the end capped polysiloxane of hydroxyl (or vinyl).High-temperature silicon disulfide rubber is according to the difference of used vulcanizing agent, and its sulfuration mechanism can be divided into free radical type sulfuration and the sulfuration of silicon hydrogen add-on type again, and cross-linked rubber correspondingly is called peroxidation type and add-on type.The basic glue that present high temperature vulcanized mode is used all is the polysiloxane that contain vinyl, and reactive group is a vinyl.Referring to Li Guangliang, " organosilicon macromolecule chemistry ", Science Press, Beijing, 1998, P122-145.
Peroxide crosslinking is the vulcanization of first kind of success of silicon rubber, in silicon rubber industrial production and application, also be the most frequently used at present, utilize decomposes such as benzoyl peroxide, ditertiary butyl peroxide to generate free radical, free radical is taken out hydrogen and is generated high molecular free radical, and two high molecular free radical couplings generate crosslinked.Require the big 40-60 ten thousand of molecular weight with the high-temp glue of peroxide cure, the distribution of molecular weight bigger just can obtain big intensity, molecular weight is bigger, then viscosity is difficult to too greatly and filler and linking agent mix, and disperses badly, influences performance.And the degradation production of the initiator of such cross-linking system often is difficult to eliminate, and leaving over influences high-temperature behavior in the glue; The gained network structure is random entirely; The flame retardant properties of this cross-linked rubber is not high yet; Some filler can absorb free radical retardance free radical curing to carry out etc., and this kind vulcanization also is difficult to prove effective under some occasion.
Addition-crosslinked is to realize under the catalysis of platinum complex containing the rubber of vinyl and the linking agent of silicon hydrate.But addition reaction of silicon with hydrogen often is accompanied by side reaction, as 2 additions, double-bond shift, reduction addition, produce hydrogen and with other group exchange etc.Silicon hydrogen addition catalyst solubleness in glue will be got well; Catalysis speed is wanted suitably will guarantee that time enough carries out mixing processing, is avoided solidifying in advance in operation shape that can not get expecting and character.Sometimes need add retarding agent, make catalyzer, and the addition of silicon hydrogen be carried out in the decomposition of curing temperature retarding agent in the katalysis of room temperature unable to get up.The addition-crosslinked precious metal that needs is made addition catalyst, and reaction finishes and can't reclaim, and remains in the cross-linked rubber,, can damage the cross-linking system of cross-linked rubber under certain condition; In addition, the trace platinum catalyzer of crosslinked usefulness is very sensitive to impurity (can form the compound of dentate as sulphur, phosphorus, ammonia etc. with platinum), and very easily " poisoning ", and lose catalytic activity, even can not vulcanize in some cases, so that can not adopt the addition vulcanization mode.
The research emphasis of high-temperature silicon disulfide rubber mainly concentrates on and how to improve synthesis technique and prepare high performance silicon rubber in recent years, improve aspects such as physical strength and thermal stability, and all be based on existing peroxide crosslinking and the addition-crosslinked system of silicon hydrogen, lack the new Study of crosslinking system of exploitation.Relevant report is referring to government official's will " the external organosilicon industrial progress of 2000-2001 ", organosilicon material, 2002,16 (1), 27-31; Zhou Qin, Zhang Aixia, " the domestic organosilicon progress of 2001-2002 ", organosilicon material, 2002,16 (6), 28-35.Although existing cross-linking system has been obtained widespread use, all be difficult to be competent at for two kinds of crosslinking methods of some special occasion.Therefore, studying new cross-linking system, and then improve the performance of silicon rubber, enlarge the Application Areas of silicon rubber, is an important directions of silicon rubber research.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of isocyanate-crosslinked high-temperature silicon disulfide rubber and preparation method thereof is provided.
New type high temperature sulphurated siliastic material component of the present invention is as follows, is weight part:
The aminoalkylpolysiloxanes rubber, molecular weight 300,000～400,000 100 part
30～65 parts of thermal silicas
0.2～4.0 part of masked isocyanate
The molecular formula of above-mentioned aminoalkylpolysiloxanes (ATPS) rubber is as follows:
m＝1，2，3...；n＝1，2，3...
The intrinsic viscosity of above-mentioned aminoalkylpolysiloxanes (ATPS) rubber is: 140 ± 2cm
3/ g.Using Ubbelohde viscometer, is solvent with toluene, measures down at 25 ℃ ± 0.1 ℃.
Above-mentioned aminoalkylpolysiloxanes (ATPS) rubber is: octamethylcyclotetrasiloxane (D
4) with Tetramethylammonium hydroxide silicon alkoxide catalyst mix, the dehydration deoxygenation, heating for dissolving gets with ammonia alkyl cyclic tetrasiloxane and the copolymerization of sily oxide balance again.
Above-mentioned aminoalkylpolysiloxanes (ATPS) rubber preparation method step is as follows: with 100-200 part octamethylcyclotetrasiloxane (D
4) put into the polymerization cup with 0.1-0.5 part Tetramethylammonium hydroxide silicon alkoxide catalyzer (alkali glue), decompression dehydration deoxygenation 0.5-5 hour is heated to 50～90 ℃, logical N
2Bubbling.After the silicon alkoxide dissolving, add 1-10 part ammonia alkyl cyclic tetrasiloxane and 0.01-0.1 part sily oxide, at N
2After mixing under the bubbling,, 130-180 ℃ of following analysing silicon alkoxide 0.5-3 hour, remove low-boiling-point substance then afterwards, obtain the water white transparency high-viscosity polymer 90-120 ℃ of following balance copolymerization 5-24 hour.Amino content is 0.1-1.0mol/100g, and molecular weight is 30-40*10
4G/mol.
Above-mentioned masked isocyanate is selected the small molecules isocyanate compound or the polymeric polyisocyanate of multiple functional radical for use, after reducing its activity with encapsulant and isocyanic ester radical reaction, uses as linking agent.As the Blocking of Isocyanates agent sodium bisulfite, aromatic amine, triol, acid amides, phenol, lactan, heterogeneous ring compound, hydrocyanic acid or sulphite etc. are arranged, referring to Li Shaoxiong, Zhu Lvmin, " urethane resin ", Jiangsu science tech publishing house, Nanjing, 1992,78.
The chemically reactive of isocyanate compound is very strong, and it is the fastest to contain in the compound of reactive hydrogen amine and its speed of response, at room temperature can react with amine.Because speed of response is too fast, to such an extent as to can not carry out as the mixing course of processing of silicone rubber crosslinking agent on mixing roll with it.Come for overcoming this shortcoming through reactive method that experimental study adopts masked isocyanate to reduce isocyanic ester.Masked isocyanate is very stable when room temperature, does not react during with the preparation of other active hydrogen compounds, can guarantee to make linking agent when the mixing silicon rubber with it, and each component is mixing evenly.Treat with glue mixing evenly after, the isocyanate groups that can dissociate again under suitable condition recovers its reactivity, reacts with amino, forms the urea key and makes silicone rubber crosslinking.
The preferred thermal silica of the present invention is reinforcing filler, other materials such as light calcium carbonate, diatomite etc. also can be used for the present invention, referring to Bo Ruidesen, elastomeric material and compound, London: Ai Er Swail, 1988,265 (Brydson JA.Rubber Materials and Their Compounds[M] .London:Elsevier, 1988,265).
The preparation of new type high temperature sulphurated siliastic of the present invention comprises rubber, reinforcing filler are cooperated with isocyanate crosslinking or additive (the same prior art of additive) that through mixing, mold pressing is high temperature vulcanized, and postcure can obtain the sulphurated siliastic of high comprehensive performance.The preparation method the invention provides following method by prior art:
Adopt the processing of open type dual-roller rubber mixing machine, roller temperature is a room temperature.At first the aminoalkylpolysiloxanes rubber is added on the roller for 100 parts, machines, make its bag roller after, add 30～65 parts of reinforcing fillers, the mixing operating time is relevant with amount of filler, generally at 25～60 minutes.Mixing uniform sizing material adds 0.2～4.0 part/100 parts rubbers of linking agent, thin-pass 10 times, sheet under the clot after 8～10 thin-passes.On vulcanizing press, carry out one step cure.The one step cure condition is: under the 29.4MPa pressure, and 130～160 ℃ * 0.5～1.5 hour; Post vulcanization carries out in the baking oven of tape drum wind, and condition is: 130～180 ℃ * 5～20 hours.
New type high temperature sulphurated siliastic preparation method distinguishing feature of the present invention is that rubber unvulcanizate can deposit the long period, and crosslinking reaction only need heat and can carry out, and it is little to be affected by the external environment, and helps enlarging the range of application of silicon rubber.The present invention has carried out systematic research to the key influence factor of each cross-linking system reaction as dosage of crosslinking agent, curing temperature and curing time etc., has obtained optimum preparating condition, and verifies by the crosslinking degree of measuring cross-linked rubber.The high comprehensive performance of the silicon rubber of the isocyanate-crosslinked system of the present invention has reached the requirement of ordinary silicon rubber applications, can be used for processing various silastic products.
The present invention proposes to introduce at the polysiloxane side chain technical scheme of active ammonia alkyl and suitable multi-functional linking agent prepared in reaction sulphurated siliastic, develop new silicone rubber crosslinking system, to remedy peroxide crosslinking and addition-crosslinked two kinds of deficiencies that system exists, successfully having solved prior art exists the residual peroxide initiator to influence silicon rubber performance and silicon hydrogen addition catalyst problems such as " poisonings " under some occasions, enlarge the range of application of silicon rubber, advance the application and development of silicon rubber.
(4) embodiment
Embodiment 1: the small molecules isocyanate compound of multiple functional radical is as linking agent
The high-temperature silicon disulfide rubber material component is as follows, is weight part: 100 parts of aminoalkylpolysiloxanes rubbers, 50 parts of thermal silicas and 1 part of dead front type vulcabond.
The preparation of aminoalkylpolysiloxanes rubber: with 100 parts of octamethylcyclotetrasiloxane (D
4) put into the polymerization cup with 0.3 part of Tetramethylammonium hydroxide silicon alkoxide catalyzer (alkali glue), decompression dehydration deoxygenation 4 hours is heated to 80 ℃, logical N
2Bubbling.After the silicon alkoxide dissolving, add 3 parts of ammonia alkyl cyclic tetrasiloxanes and 0.03 part of sily oxide, at N
2After mixing under the bubbling,, 130-180 ℃ of following analysing silicon alkoxide 2 hours, remove low-boiling-point substance then afterwards, obtain the water white transparency high-viscosity polymer 90-120 ℃ of following balance copolymer-1 8 hours.
The dead front type vulcabond: encapsulant sodium bisulfite and di-isocyanate reaction make.
The preparation method of high-temperature silicon disulfide rubber: adopt the processing of open type dual-roller rubber mixing machine, roller temperature is a room temperature.At first the aminoalkylpolysiloxanes rubber is added on the roller for 100 parts, machines, make its bag roller after, 50 parts of filler thermal silicas, mixing 40 minutes.Mixing uniform sizing material adds 1 part of linking agent dead front type vulcabond, thin-pass 10 times, sheet under the clot after 8 thin-passes.On vulcanizing press, carry out one step cure.One step cure: 130 ℃ * 0.5 hour, 29.4MPa; In the baking oven of tape drum wind, carry out postcure: 130 ℃ * 8 hours.
Performance index: hardness 56ShA, tensile strength 8.7MPa, tear strength 22.6kN/m, elongation at break 401.6%, stretch surely modulus (100%, MPa) 1.7MPa, outward appearance is the water white transparency shape.
Embodiment 2: the small molecules isocyanate compound of multiple functional radical is as linking agent
The high-temperature silicon disulfide rubber material component is as follows, is weight part: 100 parts of aminoalkylpolysiloxanes rubbers, 40 parts of thermal silicas and 1 part of dead front type vulcabond.
Aminoalkylpolysiloxanes rubber preparation method such as embodiment 1.
The preparation method of high-temperature silicon disulfide rubber such as embodiment 1, difference is that the add-on of thermal silica is 40 parts.
Performance index: hardness 44ShA, tensile strength 7.6MPa, tear strength 17.1kN/m, elongation at break 365.2%, stretch surely modulus (100%, MPa) 1.0MPa, outward appearance is the water white transparency shape.
Embodiment 3: polymeric polyisocyanate is as linking agent
The high-temperature silicon disulfide rubber material component is as follows, is weight part: 100 parts of aminoalkylpolysiloxanes rubbers, 55 parts of thermal silicas and 2 parts of dead front type polyphenyl polyisocyanates (PAPI).
Aminoalkylpolysiloxanes rubber preparation method such as embodiment 1, the dead front type polyphenyl polyisocyanate is made by encapsulant sodium bisulfite and polyphenyl polyisocyanate reaction.The preparation method of high-temperature silicon disulfide rubber such as embodiment 1, different is one step cure 150 ℃ * 0.5 hour, post vulcanization 150 ℃ * 6 hours.
Performance index: hardness 56ShA, tensile strength 7.6MPa, tear strength 21.5kN/m, elongation at break 371.2%, outward appearance is light yellow transparence.
Embodiment 4: polymeric polyisocyanate is as linking agent
The high-temperature silicon disulfide rubber material component is as follows, is weight part: 100 parts of aminoalkylpolysiloxanes rubbers, 45 parts of thermal silicas and 2 parts of dead front type polyphenyl polyisocyanates (PAPI).
Aminoalkylpolysiloxanes rubber preparation method such as embodiment 1.
The preparation method of high-temperature silicon disulfide rubber such as embodiment 3, difference is that the add-on of thermal silica is 45 parts.
Performance index: hardness 49ShA, tensile strength 5.5MPa, tear strength 17.5kN/m, elongation at break 293.6%, outward appearance is light yellow transparence.
Claims (5)
1. high-temperature silicon disulfide rubber is characterized in that, material component is as follows, is weight part:
The aminoalkylpolysiloxanes rubber, molecular weight 300,000～400,000 100 part
30～65 parts of thermal silicas
0.2～4.0 part of masked isocyanate.
2. high-temperature silicon disulfide rubber as claimed in claim 1 is characterized in that, described aminoalkylpolysiloxanes intrinsic viscosity is: 140 ± 2cm
3/ g uses Ubbelohde viscometer, is solvent with toluene, measures down at 25 ℃ ± 0.1 ℃, and the molecular formula of rubber is as follows:
m＝1，2，3...；n＝1，2，3...。
3. high-temperature silicon disulfide rubber as claimed in claim 1, it is characterized in that, described aminoalkylpolysiloxanes rubber is: octamethylcyclotetrasiloxane and Tetramethylammonium hydroxide silicon alkoxide catalyst mix, the dehydration deoxygenation, heating for dissolving, with ammonia alkyl cyclic tetrasiloxane and the copolymerization of sily oxide balance and get, amino content is 0.1-1.0mol/100g again.
4. high-temperature silicon disulfide rubber as claimed in claim 1, it is characterized in that described masked isocyanate is selected the small molecules isocyanate compound or the polymeric polyisocyanate of multiple functional radical for use, after reducing its activity, use as linking agent with encapsulant and isocyanic ester radical reaction.
5. the preparation method of high-temperature silicon disulfide rubber, comprise rubber, reinforcing filler and isocyanate crosslinking, or cooperate with additive again, through mixing, mold pressing is high temperature vulcanized, and postcure is characterized in that, adopt the processing of open type dual-roller rubber mixing machine, roller temperature is a room temperature, at first the aminoalkylpolysiloxanes rubber is added on the roller for 100 parts, machines, after making its bag roller, add 30～65 parts of reinforcing filler thermal silicas, mixing time 25～60 minutes, mixing uniform sizing material is after 8～10 thin-passes, add 0.2～4.0 part of linking agent masked isocyanate, thin-pass 10 times, sheet under the clot carries out one step cure on vulcanizing press, the one step cure condition is: under the 29.4MPa pressure, and 130～160 ℃ * 0.5～1.5 hour; Post vulcanization carries out in the baking oven of tape drum wind, and condition is: 130～180 ℃ * 5～20 hours.
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| CN101351574B (en) * | 2005-12-28 | 2010-09-29 | 杰富意钢铁株式会社 | Electromagnetic steel sheet having insulating coating film and method for producing same |
| CN109875551A (en) * | 2019-02-27 | 2019-06-14 | 中山优感科技有限公司 | Small flexible dry-type electrode of a kind of contact impedance and preparation method thereof |
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