CN109135293A - A kind of dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
A kind of dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L83/04—Polysiloxanes
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- C08L75/06—Polyurethanes from polyesters
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Abstract
The present invention provides a kind of dynamic vulcanization silicon rubber/Thermoplastic polyurethane elastomer materials and preparation method thereof, in parts by weight, vinyl polysiloxane: 100 parts, thermoplastic polyurethane elastomer: 10-500 parts, compatilizer: 3-30 parts, containing hydrogen silicone oil: 0.1-15 parts, platinum group catalyst: 0.1-100ppm (content of the pt atom in vinyl polysiloxane and containing hydrogen silicone oil), anti-poisoning dose: 0.1-20 part.Hydrogen, simple process, safety are not generated during the preparation process.This product combines the advantages of two kinds of materials of silicon rubber and TPU, with excellent surface feel, there is excellent adhesiveness with PC, PC/ABS, ABS etc., it is readily extruded and injection molding, platinum group catalyst additive amount is lower during the preparation process, product has both excellent durable service performance and lower cost, can be widely applied to require the fields such as the wearable, electric equipment products of relatively high intelligence.
Description
Technical field
The present invention relates to a kind of dynamic vulcanization silicon rubber/Thermoplastic polyurethane elastomer materials and preparation method thereof, belong to heat
Thermoplastic elastomer material production technical field.
Background technique
Dynamic vulcanization refers to that rubber phase and thermoplastic resin crosslink reaction in melt blending, while cutting in high temperature height
Under the action of cutting, crosslinking rubber is cut into micron-sized particle and is dispersed in resin.The dynamic vulcanization heat of this method preparation
Thermoplastic elastic (TPV) is not only with the physical mechanical property of thermoset rubber, but also the flow processability with thermoplastic, than
The thermoplastic elastomer (TPE) of simple blend has preferably processing and service performance, has easy processing, can be recycled, comprehensive performance
The advantages that excellent, is widely used to the neck such as automobile industry, building materials, electronic apparatus, health care and consumer appliance at present
Domain.TPU has been had both using the elastomeric material TPSiV of silicon rubber and the preparation of thermoplastic polyurethane elastomer (TPU) dynamic vulcanization
Wearability, toughness, repeatable processability and flexibility, ultraviolet light, the chemical stability of silicon rubber etc., it is also sliding with silk
Sense of touch, good coloring and color fastness, (acrylonitrile-butadiene-styrene (ABS) is copolymerized with PC (polycarbonate), PC/ABS, ABS
Object) etc. there is excellent adhesiveness, be readily extruded and injection molding, intelligence is wearable, has more in electric equipment products
It is widely applied.
The cross-linking system of silicon rubber includes peroxide crosslinking, dehydrogenation crosslinking and addition-crosslinked three kinds of crosslinking methods at present.
Wherein peroxide can not only make silicon rubber vulcanization be crosslinked, while also result in the crosslinking of TPU, so that TPSiV material does not have
Standby processability, therefore can not be as the raw material of TPU base TPSiV using the silicon rubber that peroxide is vulcanized.
United States Patent (USP) US6153691 is passed through dynamic using the organopolysiloxane and thermoplastic polyurethane elastomer of silanol sealing end
State vulcanization method prepare thermoplastic silicone elastomers TPSiV, under the catalyst action of organic carboxyl acid tin, by silanol with
The dehydrogenative condensation of containing hydrogen silicone oil reacts to carry out the crosslinking of organopolysiloxane, and the TPU base TPSiV prepared by this method is produced
The degree of cross linking of product is higher, and resilience performance is excellent, but product can generate hydrogen during condensation reaction, needs to carry out hydrogen
Recycling, cause the production technology of product complex, while being easy to produce safe risk.
The Li Shanliang of Guangdong University of Technology passes through dynamic sulphur using vinylsiloxane rubber and thermoplastic polyurethane elastomer
The method of change prepares thermoplastic silicone elastomers TPSiV, under the catalytic action of platinum group catalyst, passes through vinylsiloxane rubber
In vinyl and containing hydrogen silicone oil addition reaction come carry out silicon rubber dynamic vulcanization (Li Shanliang, polyurethane/silicon rubber dynamic
The preparation of sulfuration thermoplastic elastomer and performance study Guangdong University of Technology master thesis 2011), at present in add-on type
In the catalyst system of polysiloxanes, other than platinum group catalyst, other metallic catalysts such as cobalt, ruthenium, rhodium etc., these catalyst
Catalytic efficiency is lower, and cost is also higher than platinum group catalyst, therefore the addition silicon rubber catalyst of industrial applications at present
Have a catalyst of platinum group, but platinum group catalyst has a biggish weakness, i.e., with containing elements such as N, P, S organic matter or Sn,
When the ionic compound of the heavy metals such as Pb, Hg, Bi, As and unsaturated compounds contact containing alkynyl, these elements or compound
There are lone pair electrons, easily combined with the d orbital electron of platinum, form strong adsorption bond, makes platinum group catalyst poison deactivation, it is special
It is not the ionic compound of heavy metal, may result in the permanent failure of platinum group catalyst, platinum group catalyst is easy poisoning and makes
Silicone cross degree is lower or cannot be crosslinked, the product of low crosslinking degree not only results in TPSiV product permanent compression set
Become larger, while the surfaces of tacky of product can be made, seriously affects the surface feel of material.TPU can add one in the process of production
The catalyst of quantitative organic tin accelerates the reaction speed of product, but the catalyst of organic tin will lead to platinum group catalysis
The poisoning of agent influences the activity of platinum group catalyst, at present can only be by the method for a large amount of platinum group catalyst of addition, to make up
Influence of the TPU catalyst to platinum group catalyst, but this content that will lead to catalyst total in TPSiV system is higher, a side
Face can accelerate the degradation of TPU continuous phase in TPSiV, influence the durable usability of TPSiV；Simultaneously because the price of platinum group catalyst
Valuableness, adding a large amount of platinum group catalyst will increase the cost of TPU base TPSiV product.
Therefore it needs to develop a kind of new TPSiV material.
Summary of the invention
The purpose of the present invention is in view of the deficiencies in the prior art and insufficient, a kind of high-durability, low cost are developed
Dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer product.
To achieve the above objectives, technical scheme is as follows:
A kind of dynamic vulcanization silicon rubber/Thermoplastic polyurethane elastomer material is prepared by the raw material for including following components, with
Parts by weight meter:
Vinyl polysiloxane: 100 parts
Thermoplastic polyurethane elastomer: 10-500 parts, preferably 30-300 parts
Compatilizer: 3-30 parts, preferably 5-20 parts
Containing hydrogen silicone oil: 0.1-15 parts, preferably 0.5-10 parts
Anti-poisoning dose: 0.1-20 part, preferably 0.5-5 parts
Platinum group catalyst: in terms of pt atom, the dosage of platinum group catalyst is that pt atom accounts for rubber composition substance
The 0.1-100ppm of amount, preferably 10-80ppm,
The silicone rubber compound refers to vinyl polysiloxane and containing hydrogen silicone oil.
The structural formula of heretofore described vinyl polysiloxane are as follows:
Wherein, R1And R2It is same or different, it can be the substituted or unsubstituted alkyl containing 1-10 carbon atom, contain 6-
The substituted or unsubstituted aryl group of 10 carbon atoms, substituent group can be phenyl, fluorine-based, chloro, ethyl, ethylidene, first
One of oxygroup is a variety of；R1And R2It is preferred that methyl, ethyl, phenyl, trifluoro propyl；R3For vinyl or methyl.Preferably,
Vinyl polysiloxane selected from contents of ethylene is 0.04-10mol%, vinyl number >=2 in individual molecule, room temperature (25
DEG C) vinyl polysiloxane of viscosity 1000-15000 centipoise；More preferable contents of ethylene is 0.06-9mol%, room temperature viscosity
The vinyl polysiloxane of 2000-13000 centipoise, most preferably contents of ethylene are 0.08-8mol%, room temperature viscosity 2500-
The vinyl polysiloxane of 12000 centipoises.Select the vinyl polysiloxane of certain viscosity that can make TPU and the poly- silicon of vinyl
Oxygen alkane is kneaded more uniform during mixing, and uniform co-mixing system can significantly improve the catalysis effect of platinum group catalyst
Rate advantageously reduces the dosage of platinum group catalyst.Suitable vinyl polysiloxane such as Anhui Ai Yueta silicone oil Co., Ltd
IOTA1000, IOTA3000, IOTA5000,110-1,110-2,110-3, GY-131 of Jinan gold brightness chemical industry, Hangzhou Jiande are poly-
Close 204-5000,204-10000,204-60000,205-3000,205-10000 etc. of new material.
Thermoplastic polyurethane elastomer (TPU) of the present invention is the thermoplastic polyurethane bullet of tensile strength 10-45MPa
Property body, can be polyester-type thermoplastic polyurethane, polyether thermoplastic polyurethane, polycarbonate type thermoplastic polyurethane and gathers oneself
One of lactone type thermoplastic polyurethane is a variety of；The polyethers and/or polyester-type thermoplasticity of preferred tensile strength 12-42MPa
Polyurethane elastomer；The most preferably polyester-type thermoplastic polyurethane elastomer of tensile strength 15-40MPa.TPU is as TPSiV's
Continuous phase, preferably the polyester-type TPU with certain tensile strength can not only guarantee that the TPSiV of dynamic vulcanization is with higher
Stretching and tearing strength simultaneously because polyester-type TPU has more excellent durable service performance, therefore can also significantly improve
The durable usability of TPSiV.
Thermoplastic polyurethane elastomer of the present invention is by least one polyisocyanates, at least one polyalcohol and extremely
A kind of few chain extender reaction preparation.
Polyisocyanates of the present invention be selected from one of aromatic polyisocyanate and aliphatic polyisocyante or
It is a variety of；The polyisocyanates includes but is not limited to 4,4'- methyl diphenylene diisocyanate (4,4'-MDI), 2,4'- hexichol
Dicyclohexylmethane diisocyanate (2,4'-MDI), 2,2'- methyl diphenylene diisocyanate (2,2'-MDI), phenylenedimethylidyne two are different
It is cyanate (XDI), 1,5- naphthalene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), toluene di-isocyanate(TDI) (TDI), different
Isophorone diisocyanate (IPDI), 1,4- cyclohexyl diisocyanate (CHDI), hexamethylene diisocyanate (HDI), the last of the ten Heavenly stems
Alkane -1,10- diisocyanate and dicyclohexyl methyl hydride -4,4'- diisocyanate (H12MDI one of) or a variety of, preferably 4,
4'- methyl diphenylene diisocyanate.
Polyalcohol of the present invention is selected from polyester polyol, poly-lactone polyol, polycarbonate polyol and polyether polyols
One of alcohol is a variety of, preferably polyester polyol and/or polyether polyol, most preferably polyester polyol.
Polyester polyol of the present invention can by dihydric alcohol and dicarboxylic acids, dicarboxylic acids acid anhydrides or dicarboxylic esters into
Row esterification or ester exchange reaction are prepared.The number-average molecular weight (Mn) of the polyester polyol is 500-10000, preferably
700-5000, more preferably 750-4000；Acid value is 0-1.0mgKOH/g, preferably 0.1-0.5mgKOH/g.
Dihydric alcohol used in polyester polyol of the present invention preparation is aliphatic and/or aromatic diol, excellent
It is selected as one of dihydric alcohol or a variety of with 2 to 12 carbon atoms, more preferable ethylene glycol, 1,2-PD, 1,3- the third two
Alcohol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 2,2- dimethyl -1,3- propylene glycol, 1,4- hexamethylene
One of dimethanol, decanediol and dodecanediol are a variety of, further preferred 1,4-butanediol.
Dicarboxylic acids, dicarboxylic acids acid anhydrides or dicarboxylic esters used in polyester polyol of the present invention preparation be
Aliphatic and aromatic dicarboxylate or one of dicarboxylic acids acid anhydrides or dicarboxylic esters or a variety of；Preferably have 4 to 15
One of dicarboxylic acids, dicarboxylic acids acid anhydrides or dicarboxylic esters of a carbon atom are a variety of, more preferably phthalic acid, benzene
Dicarboxylic acid anhydride, repefral, dimethyl terephthalate (DMT), succinic acid, glutaric acid, adipic acid, pimelic acid, pungent two
Acid, azelaic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid, terephthalic acid (TPA), cyclohexyl dicarboxylic acid, phthalic anhydride and four
One of hydrogen phthalic anhydride is a variety of；Further preferably adipic acid, phthalic anhydride and tetrahydrophthalic acid
One of acid anhydride is a variety of.
In the preparation process of polyester polyol of the present invention, the dihydric alcohol and dicarboxylic acids, dicarboxylic acids acid anhydrides or
The molar ratio of dicarboxylic esters is preferably 1.0-3.0, more preferable 1.02-2.0.
Poly-lactone polyol of the present invention is preferably polycaprolactone polyol, is existed by 6-caprolactone monomer and initiator
It is prepared under catalyst initiation.The number-average molecular weight (Mn) of the polycaprolactone polyol is preferably 500-3000, more
Preferably 1000-2000.
Used initiator in poly-lactone polyol preparation of the present invention is one in diamines, hydramine and polyalcohol
Kind is a variety of, preferably ethylene glycol, 1,2-PD, 1,3-PD, diethylene glycol, 1,3-BDO, 1,4-butanediol, 1,
5- pentanediol, neopentyl glycol, 1,6-HD, 1,4- cyclohexanediol, trimethylolpropane, pentaerythrite, 3,3 '-two chloro- 4,
One of 4 '-diaminodiphenylmethane, diethyl toluene diamine, monoethanolamine and diethanol amine are a variety of；More preferably second
One of glycol, 1,4- butanediol, neopentyl glycol, diethylene glycol, trimethylolpropane (TMP) and pentaerythrite are a variety of.
Phosgenation has can be used in polycarbonate polyol of the present invention, carbon dioxide adjusts copolymerization method, cyclic carbonate
Ring-opening polymerisation method or ester-interchange method synthesis obtain.
Polycarbonate polyol of the present invention preferably passes through dihydric alcohol and carbonic ester carries out ester exchange reaction synthesis.
During ester-interchange method polycarbonate synthesis polyalcohol of the present invention, the dihydric alcohol is preferably 1,2- second two
One of alcohol, 1,4- butanediol (BDO), 1,5- pentanediol (PDO) and 1,6-HD (HDO) are a variety of；More preferably 1,
4- butanediol (BDO) and/or 1,5- pentanediol (PDO).The carbonic ester is preferably dimethyl carbonate and diethyl carbonate；It is more excellent
It is selected as dimethyl carbonate.
The number-average molecular weight (Mn) of polycarbonate polyol of the present invention is 500-4000, preferably 1000-3000.
Polyether polyol of the present invention is to be reacted by initiator with the epoxide containing 2 to 6 carbon atoms, preparation
Obtained polyether polyol.
The number-average molecular weight (Mn) of polyether polyol of the present invention is 500 to 10000, preferably 700-4000.
Initiator used in polyether polyol preparation process of the present invention is small molecule polyol, small molecule polyamine
With one of small molecule hydramine or a variety of；The initiator preferably is selected from water, propylene glycol, glycerol, trimethylolpropane, ethylenediamine
One of pentaerythrite, xylitol, triethylene diamine, sorbierite, ethylene glycol, bisphenol-A and toluenediamine are a variety of；More preferably
For one of water, propylene glycol and glycerol or a variety of.
Epoxide used in polyether polyol preparation process of the present invention is preferably ethylene oxide, propylene oxide
With one of tetrahydrofuran (THF) or a variety of.
Polyether polyol of the present invention preferably is selected from polyethylene glycol, the propylene oxide of ethylene oxide and glycol reaction preparation
Polypropylene glycol or water that preparation is reacted with propylene glycol react the polytetramethylene ether diol of preparation with tetrahydrofuran (THF)
(PTMEG), the reaction product copolyether of THF and ethylene oxide or THF and propylene oxide；Preferred polyether polyol is poly- four
Methylene ether glycol (PTMEG).
The molar ratio of polyisocyanates and polyalcohol of the present invention is 0.95-1.10, preferably 0.96-1.02.
Chain extender of the present invention is selected from one of glycol or a variety of with 2 to 10 carbon atoms, preferably ethylene glycol,
Diethylene glycol, propylene glycol, dipropylene glycol, 1,4- butanediol, 1,6-HD, 1,3 butylene glycol, 1,5- pentanediol, 1,4- hexamethylene
Glycol, (ethoxy) one of the ether and neopentyl glycol or a variety of of quinhydrones two, further preferred 1,4-butanediol.
The dosage of chain extender of the present invention is the 3%-25% based on polyisocyanates Yu polyalcohol gross mass, preferably
5%-20%.
The specific product of TPU of the present invention can be selected: WHT-1180, WHT- of Wanhua Chemical Group Co., Ltd.
1185、WHT-1190、WHT-1195、WHT-1570、WHT-1580、WHT-1585、WHT-1590、WHT-1595、WHT-8180、
WHT-8185, WHT-8190, WHT-8195, WHT-8285 etc..
Platinum group catalyst of the present invention be selected from platinum black, platinum chloride, the mixture of chloroplatinic acid and monohydric alcohol, chloroplatinic acid with
One of the complex compounds of alkenes compounds, acetoacetate platinum are a variety of, preferably the mixture of chloroplatinic acid and monohydric alcohol, chlorine platinum
One of acid and the complex compound of alkenes compounds are a variety of, most preferably the complex compound of chloroplatinic acid and alkenes compounds,
In, the monohydric alcohol can be methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, octanol etc., alkenes compounds can be ethylene,
Cyclohexene and its derivative, vinyl polysiloxane etc..The specific product of platinum group catalyst has: Japanese SHIN-ETSU HANTOTAI's chemical industry strain formula
The CAT-56 of commercial firm, the DC4000 of DOW CORNING organosilicon, ACS-Pt-100 of Shanghai Xi Bao new high-tech material Co., Ltd etc..
Heretofore described compatilizer is selected from silicane-modified polyurethane, polysiloxane grafted ethylene-vinyl acetate (EVA) altogether
Polymers, hydrogenated styrene block thermoplastic polyurethane copolymer, Polyolefin Grafted Maleic Anhydride, ethylene propylene diene rubber are grafted Malaysia
One of acid anhydrides, polyolefin elastomer grafted maleic anhydride are a variety of, preferably silicane-modified polyurethane, hydrogenated styrene block
One of thermoplastic polyurethane copolymer, polysiloxane grafted EVA or a variety of, most preferably silicane-modified polyurethane.Compatilizer tool
The product of body has Pursil-TSPU80, Pursil-TSPU83 of Royal DSM chemistry；The S5265 etc. of Kuraray.
Its structural formula of heretofore described containing hydrogen silicone oil are as follows:
Wherein X1For methyl or hydrogen, X2For the alkyl group containing 1-10 carbon atom, X2It is preferred that methyl, ethyl, propyl, different
Propyl, butyl etc..The mass fraction for the hydrogen atom that containing hydrogen silicone oil is preferably connected with Si is 0.01-1.66%, and room temperature viscosity is 1-
The containing hydrogen silicone oil of 500 centipoises；The mass fraction for the hydrogen atom being more preferably connected with Si is 0.05-1.6%, and room temperature viscosity is 5-
The containing hydrogen silicone oil of 450 centipoises；The mass fraction for the hydrogen atom being most preferably connected with Si is 0.08-1.58%, and room temperature viscosity is 10-
The containing hydrogen silicone oil of 400 centipoises.Specific market product have Dongguan, Guangdong city Tian An silicon rubber Science and Technology Ltd. TNH-0.13,
TNH-0.18,TNH-0.36,TNH-0.75,TNH-1.2,TNH-1.6；The CG- of Zhonglan Chenguang Chemical Institute Co., Ltd.
0.19,CG-0.38,CG-0.75,CG-1.1,CG-1.5；GY-0.18, GY- of Shanghai silicon friend scientific and technological new material Co., Ltd
0.25, GY-0.5, GY-0.8, GY-1.2 etc..
The anti-poisoning dose of the present invention compound system for organo-aluminum compound and hydrazide kind compound, organo-aluminium chemical combination
For the mass ratio of object and hydrazide kind compound between 1:1 to 5:1, organo-aluminum compound includes aluminium isopropoxide, acetyl acetone
Aluminium, diacetyl acetonyl aluminum isopropoxide etc.；Hydrazide kind compound includes N, and N '-two replaces two hydrazine of oxalyl group, the Asia N- bigcatkin willow
Base-N ' salicylyl hydrazine, 3- salicylamide base -1,2,4- triazole, oxalyl hydrazine etc., wherein the N, N '-two replace oxalyl group
Two hydrazines include N, bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionyl] hydrazines of N '-etc.；Anti-poisoning dose of preferred acetyl acetone aluminium
Replace the compound system of two hydrazine of oxalyl group with N, N '-two.Organo-aluminum compound can be Japanese river and grind fine chemistry industry
Kawaken A (w) (acetyl acetone aluminium), high-purity acetyl acetone aluminium of Tianjin He Zhi Chemical Co., Ltd., Dalian University of Science & Engineering are normal
The high puring aluminium isopropoxide etc. of ripe Co., Ltd of research institute；Hydrazide kind compound can be the MD1024 of BASF vapour bar fine chemistry industry
The inhibitor of (bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionyl] hydrazines of N, N ' -), Eastman Kodak Company
OABH (oxalyl hydrazine), Japanese Asahi Denka Kogyo K. K CDA-1 (3- salicylamide base -1,2,4- triazole), CDA-6
(N- salicylidene-N ' salicylyl hydrazine).Organo-aluminum compound has the function of that platinum group catalyst is prevented to be poisoned, in room temperature vulcanization silicon
The poisoning that can effectively prevent platinum group catalyst in rubbery system reduces the vulcanization time of silicon rubber, but high temperature vulcanized
In system, the individual poisoning that platinum group catalyst can not be effectively prevented using organo-aluminum compound, and the acyl that the present invention selects
Hydrazine class compound has the function of passive metal ion, can be effective by organic calorize and the compounding of object and hydrazide kind compound
The poisoning for preventing platinum group catalyst, reduce the dosage of platinum group catalyst, prevent catalysis of the excessive platinum group catalyst to TPSiV
Degradation improves the durable service performance of product.
Dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer of the present invention, optional addition vapor phase method hard charcoal
The inert fillers such as black, precipitated silica, silicone resin, silicon powder, diatomite, calcium carbonate reduce the cost of material, inert filler
Additive amount be 0-200 part, based on aforementioned formula；And/or optional addition anti-aging auxiliary agent, including the suction of antioxidant, ultraviolet light
The ageing-resistant performance that agent, light stabilizer etc. improve product is received, anti-aging additive dosage is 0-5 parts, is based on aforementioned formula.Antioxygen
Agent, UV absorbers, specific producer such as BASF vapour bar fine chemistry industry, Li Anlong, Taiwan double bond of light stabilizer etc..
In the present invention, the dynamic vulcanization silicon rubber/method for preparing thermoplastic polyurethane elastomer is as follows: according to each
Parts by weight described in component,
(1) high temperature kneading: TPU, compatilizer, vinyl polysiloxane, optional inert filler, optional anti-aging are helped
Agent, platinum group catalyst, anti-poisoning dose 150-200 DEG C at a temperature of kneading 1-20min in masticator is added, then pass through single screw rod
Extruder extruding pelletization；
(2) it is double that particle and containing hydrogen silicone oil that step (1) obtains dynamic vulcanization: are passed through into different Weightlessness equipment feedings respectively
Screw extruder, engine speed are set as 100-600 and turn/min, and melting temperature carries out dynamic sulphur under conditions of being 170-230 DEG C
Change 1-8min, pelletizing, packaging are carried out by pelletizing machine equipment, product is made.
The present invention carries out the TPSiV product that dynamic vulcanization prepares TPU base using silicone rubber material and thermoplastic polyurethane, produces
Product combine the advantages of two kinds of materials of silicon rubber and TPU, have excellent surface feel, have with PC, PC/ABS, ABS etc. excellent
Different adhesiveness, is readily extruded and injection molding；During the preparation process by using of the invention anti-poisoning dose, platinum group can be made
Catalyst loading is lower and prevents its poisoning, and product has both excellent durable service performance and lower cost, while product
Hydrogen, simple process, safety will not be generated during preparation.Product of the present invention can be widely applied to require relatively high intelligence
The fields such as the wearable, electric equipment products of energy, have significant economic and social benefit.
Specific embodiment
Below we the present invention is further elaborated in conjunction with specific embodiments, but the scope of the present invention and unlimited
In these embodiments.
The preparation step of embodiment are as follows:
(1) high temperature kneading: by TPU, compatilizer, vinyl silicon polysiloxanes, optional inert filler, optional antioxygen
Agent, platinum group catalyst, anti-poisoning dose 150-200 DEG C at a temperature of be added Dalian Hua Han rubber and plastics machine Co., Ltd X (S) N-
Kneading 5-10min in 20x30 masticator, then squeezed out by the SJ-45 single screw extrusion machine of Zhangjiagang Huaming Machinery Co., Ltd.
It is granulated；
(2) dynamic vulcanization: above-mentioned particle is passed through by NX-S50L weightlessness feeding scale, the containing hydrogen silicone oil in Japanese Kubo field
The HF-L-1 liquid weightlessness feeding scale of Wuxi Hai Feite mechanical equipment Co., Ltd feeds Nanjing Jieya Extruding Equipment Co., Ltd.
SHJ-42 double screw extruder in, engine speed is set as 300-500 and turns/min, and melting temperature is 170-230 DEG C of condition
Lower progress dynamic vulcanization 1-3min, is cut into finished particle by pelletizing machine equipment.
Then finished particle is molded into standard test piece by extra large day SA900 injection molding machine, carries out relevant test characterization, surveys
Method for testing is as follows:
Hardness is tested according to ASTM D4420
Tensile strength and elongation at break are tested according to ASTM D412
Melt index is tested according to ASTM D1238, and test condition is 200 DEG C/5kg
Compression Set is tested by ASTM D395, and test condition is 25 DEG C/24H
The test method of the degree of cross linking: weighing thermoplastic elastomer (TPE) 1g, is labeled as W1It is uncrosslinked using Soxhlet extractor drawer
Silicon rubber, the solvent of extracting is tetrahydrofuran, and the time of extracting is 168h, after the completion of extracting, by undissolved thermoplastic elastomehc
Property body is dried in vacuo for 24 hours under conditions of 90 DEG C in a vacuum drying oven, quality status stamp W2, then the degree of cross linking of TPSiV
Calculation method are as follows:
δ is the mass fraction of silicon rubber
W1For the quality of the thermoplastic elastomer (TPE) of weighing
W2For the quality of undissolved thermoplastic elastomer (TPE)
Heat aging performance test tested according to GB T312, thermal aging temperature be 121 DEG C, by test 121 DEG C/
The retention rate of the tensile strength of material evaluates the durable service performance of product under the conditions of 168H.
Raw material used in embodiment and source:
Vinyl polysiloxane is 110-2,110-3 of Jinan gold brightness chemical industry, Anhui Ai Yueta silicone oil Co., Ltd
IOTA3000, it is the vinyl polysiloxane of 9500 centipoises, contents of ethylene 0.16mol% that wherein 110-2, which is room temperature viscosity,
110-3 is that room temperature viscosity is the vinyl polysiloxane of 9000 centipoises, contents of ethylene 0.25mol%；The room of IOTA3000
Warm viscosity is 3000 centipoises, contents of ethylene 0.7mol%.
TPU is polyester-type TPU WHT-1180 of Wanhua Chemical Group Co., Ltd., WHT-1190, WHT-1195 and
Polyether-type TPU WHT-8180, wherein the tensile strength of WHT-1180 be the tensile strength of 30MPa, WHT-1190 be 36MPa,
The tensile strength of WHT-1195 is that the tensile strength of 39MPa, WHT-8180 are 25MPa.
Compatilizer is the siliceous copolymerizable thermosetting polyurethane TSPU80 and TSPU83 of Royal DSM chemistry；The hydrogen of Kuraray
Change styrene block thermoplastic's property polyurethane copolymer S5265.
Containing hydrogen silicone oil is the CG-0.38 of Dongguan, Guangdong city Tian An silicon rubber Science and Technology Ltd. TNH-0.18, middle blue morning twilight,
Wherein TNH-0.18 room temperature viscosity is 100 centipoises, the hydrogen mass fraction that is connected with Si is 0.18wt%；CG-0.38 room temperature viscosity
It is 0.38wt% for 70 centipoises, the hydrogen mass fraction being connected with Si.
Catalyst is the Japan CAT-56 of the Shin-Etsu Chemial Co., Ltd and DC4000 of DOW CORNING organosilicon, main
Ingredient be all chloroplatinic acid and vinyl polysiloxane complex compound.
The anti-poisoning dose of compound for organo-aluminum compound and hydrazide kind compound, wherein organo-aluminum compound is Japanese river
Grind the Kawaken A (w) of fine chemistry industry, the high puring aluminium isopropoxide of Dalian University of Science & Engineering Changshu Co., Ltd of research institute；Hydrazides chemical combination
Object is MD1024, the CDA-1 of Japanese Asahi Denka Kogyo K. K of BASF vapour bar fine chemistry industry, prevents that 1 is Kawaken A (w)
The compound for being 1:1 with MD1024 mass ratio；The compound that anti-2 be Kawaken A (w) and CAD-1 mass ratio is 3:1；Anti- 3 are
The compound that aluminium isopropoxide and MD1024 mass ratio are 4:1.
Inert filler is that fumed silica M-5, the antioxidant of Cabot fine chemistry industry are BASF vapour bar fine chemistry industry
Compound antioxidant B900.
The process conditions of embodiment and comparative example are as shown in table 1:
Table 1
The formula of embodiment and comparative example is as shown in table 2:
Table 2
Embodiment and the performance test results of comparative example product are as shown in table 3:
Table 3
It is compared by comparative example 1 and embodiment 1, under identical Recipe, in no anti-poisoning dose of addition
Under the conditions of, the crosslinking degree of the product of comparative example 1 is lower, and compressive deformation is larger, simultaneously because vulcanization is not exclusively, the surface of product
Tacky, feel is poor, and after being added to anti-poisoning dose, the crosslinking degree of 1 product of embodiment is significantly improved, and compressive deformation becomes smaller,
Surface feel is smooth；Ratio is carried out by comparative example 2 and embodiment 2, under identical process recipe, in comparative example 2 individually
Using organo-aluminum compound, the crosslinking degree of product is still lower, and compressive deformation is larger, in example 2 by using compounding
Anti-poisoning dose, the crosslinking degree of product significantly improves；Be compared by comparative example 3 and embodiment 3, it is identical formula and
Under technique, although the degree of cross linking of product, height catalysis can be improved merely in comparative example 3 by way of improving catalyst content
The heat aging property of product is deteriorated under agent content, affects the durable service performance of product, passes through in embodiment 3 and add in anti-
Toxic agent can improve the degree of cross linking of product under the content compared with low catalyst, have lower compressive deformation and splendid
Surface feel, while the heat aging property of product is preferable, has excellent durable usability.
Specific embodiment described above is to be done to spirit of that invention for example, be not intended to restrict the invention, all
Made any modifications, equivalent replacements, and improvements etc. within the spirit and principles in the present invention should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer, which is characterized in that by the raw material system including following components
It is standby, in parts by weight:
Vinyl polysiloxane: 100 parts
Thermoplastic polyurethane elastomer: 10-500 parts, preferably 30-300 parts
Compatilizer: 3-30 parts, preferably 5-20 parts
Containing hydrogen silicone oil: 0.1-15 parts, preferably 0.5-10 parts
Anti-poisoning dose: 0.1-20 part, preferably 0.5-5 parts
Platinum group catalyst: in terms of pt atom, the dosage of platinum group catalyst is the 0.1- that pt atom accounts for rubber composition amount of substance
100ppm, preferably 10-80ppm,
The silicone rubber compound refers to vinyl polysiloxane and containing hydrogen silicone oil.
2. dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer as described in claim 1, which is characterized in that vinyl is poly-
The structural formula of siloxanes are as follows:
Wherein, R1And R2It is same or different, it is former selected from substituted or unsubstituted alkyl, 6-10 carbon containing 1-10 carbon atom
Son substituted or unsubstituted aryl, substituent group be selected from one of phenyl, fluorine-based, chloro, ethyl, ethylidene, methoxyl group or
It is a variety of, R1And R2It is preferred that methyl, ethyl, phenyl, trifluoro propyl, R3For vinyl or methyl；
Preferably, vinyl polysiloxane selected from contents of ethylene be 0.04-10mol%, the vinyl number in individual molecule
>=2, the vinyl polysiloxane of room temperature viscosity 1000-15000 centipoise, more preferable contents of ethylene 0.06-9mol%, room temperature are glutinous
The vinyl polysiloxane of 2000-13000 centipoise is spent, most preferably contents of ethylene is 0.08-8mol%, room temperature viscosity 2500-
The vinyl polysiloxane of 12000 centipoises.
3. dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer as claimed in claim 1 or 2, which is characterized in that described
Thermoplastic polyurethane elastomer is the thermoplastic polyurethane elastomer of tensile strength 10-45MPa；Preferred tensile strength 12-42MPa
Polyethers and/or polyester-type thermoplastic polyurethane elastomer；The polyester-type thermoplastic poly ammonia of most preferably tensile strength 15-40MPa
Ester elastomer.
4. dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer as described in any one of claims 1-3, which is characterized in that
Compatilizer is selected from silicane-modified polyurethane, polysiloxane grafted ethylene-vinyl acetate copolymer, hydrogenated styrene block thermoplastic poly
Urethane copolymer, Polyolefin Grafted Maleic Anhydride, grafting maleic anhydride with ethylene propylene terpolymer, polyolefin elastomer grafted maleic
One of acid anhydride is a variety of, and preferably silicane-modified polyurethane, hydrogenated styrene block thermoplastic polyurethane copolymer, siloxanes connect
One of branch ethylene-vinyl acetate copolymer is a variety of, most preferably silicane-modified polyurethane.
5. dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer according to any one of claims 1-4, which is characterized in that
The structural formula of containing hydrogen silicone oil is as follows:
Wherein, X1For methyl or hydrogen；X2For the alkyl group containing 1-10 carbon atom, preferably methyl, ethyl, propyl, isopropyl,
Butyl；
Preferably, mass fraction of the containing hydrogen silicone oil selected from the hydrogen atom being connected with Si is 0.01-1.66%, room temperature viscosity is 1-
The containing hydrogen silicone oil of 500 centipoises, the mass fraction for the hydrogen atom being more preferably connected with Si is 0.05-1.6%, room temperature viscosity is 5-
The containing hydrogen silicone oil of 450 centipoises, the mass fraction for the hydrogen atom being most preferably connected with Si is 0.08-1.58%, room temperature viscosity is 10-
The containing hydrogen silicone oil of 400 centipoises.
6. dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer as described in any one in claim 1-5, which is characterized in that
The platinum group catalyst is selected from the network of the mixture of platinum black, platinum chloride, chloroplatinic acid and monohydric alcohol, chloroplatinic acid and alkenes compounds
Close one of object, acetoacetate platinum or a variety of, the preferably mixture of chloroplatinic acid and monohydric alcohol, chloroplatinic acid and alkenes compounds
One of complex compound or a variety of, the most preferably complex compound of chloroplatinic acid and alkenes compounds.
7. dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer as claimed in any one of claims 1 to 6, which is characterized in that
The described anti-poisoning dose compound system for organo-aluminum compound and hydrazide kind compound, organo-aluminum compound and hydrazide kind compound
Mass ratio be 1:1-5:1；
The organo-aluminum compound is selected from one of aluminium isopropoxide, acetyl acetone aluminium, diacetyl acetonyl aluminum isopropoxide
Or it is a variety of, the hydrazide kind compound is selected from N, and N '-two replaces two hydrazine of oxalyl group, N- salicylidene-N ' salicylyl hydrazine, 3- water
One of poplar amide groups -1,2,4- triazole, oxalyl hydrazine are a variety of；Anti-poisoning dose of preferred aluminium acetylacetonate and N, N '-two take
For the compound system of two hydrazine of oxalyl group.
8. such as the described in any item dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer of claim 1-7, which is characterized in that
It optionally adds inert filler and/or optionally adds anti-aging auxiliary agent, the inert filler is selected from fume colloidal silica, precipitating
One of method white carbon black, silicone resin, silicon powder, diatomite, calcium carbonate are a variety of, the anti-aging auxiliary agent be selected from antioxidant,
One of UV absorbers, light stabilizer are a variety of.
9. a kind of method for preparing the described in any item dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer of claim 1-8,
Include the following steps, according to the parts by weight:
(1) high temperature kneading: by thermoplastic polyurethane elastomer, compatilizer, vinyl polysiloxane, optional inert filler, appoint
The anti-aging auxiliary agent of choosing, anti-poisoning dose, platinum group catalyst is added kneading in masticator at a certain temperature, then squeezed by single screw rod
Machine extruding pelletization out；
(2) dynamic vulcanization: particle and containing hydrogen silicone oil that step (1) obtains are passed through into different Weightlessness equipments respectively and feed twin-screw
Extruder carries out dynamic vulcanization under certain melting temperature, carries out pelletizing by pelletizing machine equipment.
10. according to the method described in claim 9, it is characterized in that, temperature in step (1) is 150-200 DEG C, the kneading time
For 1-20min；Melting temperature is 170-230 DEG C in step (2), and the dynamic vulcanization time is 1-8min.
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