CN109694581B - Dynamic vulcanized silicone rubber/thermoplastic polyurethane elastomer material and preparation method thereof - Google Patents
Dynamic vulcanized silicone rubber/thermoplastic polyurethane elastomer material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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Abstract
The invention discloses a dynamic vulcanized silicone rubber/thermoplastic polyurethane elastomer material, which comprises the following components in parts by weight: 100 parts of thermoplastic polyurethane elastomer: 10-300 parts of an organosilicon modified thermoplastic polyurethane elastomer: 10-300 parts of hydrogen-containing silicone oil: 0.1-15 parts, and sufficient amount of platinum group catalyst; the invention also discloses a preparation method of the material. The product of the invention has particularly excellent bending resistance, and can be widely applied to the fields of intelligent wearable products, electronic and electric products and the like with higher bending requirements.
Description
Technical Field
The invention belongs to the technical field of thermoplastic elastomer material production, and relates to a dynamic vulcanized silicone rubber/thermoplastic polyurethane elastomer material and a preparation method thereof.
Background
Dynamic vulcanization means that the rubber phase and the thermoplastic resin are subjected to a crosslinking reaction during melt blending, and the crosslinked rubber is sheared into micron-sized particles to be dispersed in the resin under the action of high temperature and high shear. The dynamic vulcanization thermoplastic elastomer (TPV) prepared by the method has the physical and mechanical properties of thermosetting rubber and the flow processability of thermoplastic, has better processing and using performance compared with the simply blended thermoplastic elastomer, has the advantages of easy processing, recycling, excellent comprehensive performance and the like, and is widely applied to the fields of automobile industry, building materials, electronic and electric appliances, medical sanitation, consumer goods and the like at present.
The elastomer material TPSiV prepared by dynamically vulcanizing the silicon rubber and the thermoplastic polyurethane elastomer (TPU) has the advantages of wear resistance, toughness, repeatable processability of the TPU, softness, ultraviolet light resistance, chemical stability and the like of the silicon rubber, silky touch, good colorability and color fastness, excellent adhesiveness with PC (polycarbonate), PC/ABS, ABS and the like, easiness in extrusion and injection molding, and wide application in intelligent wearable and electronic and electrical products.
But TPSiV's resistant bending performance is than poor, and is particularly microthermal resistant bending performance is relatively poor, and TPSiV is the watchband of intelligent wrist-watch and intelligent bracelet for most typical application, and TPSiV is when the watchband as intelligent wrist-watch and intelligent bracelet, and the condition of watchband fracture takes place very easily in the use, and this very big restriction TPSiV is in wearable application in the field.
Dow Corning patent TW542849B uses vinyl silicone rubber and thermoplastic resin to prepare TPSiV by dynamic vulcanization method, wherein the base material is selected from polyolefin and polybutylene terephthalate, the patent does not mention TPU base material in the resin system of claims and examples, the main focus is that under the same formula, the tensile strength and elongation at break of TPSiV prepared by dynamic vulcanization method are at least 25% higher than those of elastomer material prepared by simple blending method, and the key index of bending resistance of TPSiV, which influences the final application of material, is not concerned.
Li of Guangdong industry university adopts vinyl silicone rubber and thermoplastic polyurethane elastomer TPU to prepare thermoplastic silicone elastomer TPSiV through a dynamic vulcanization method, under the catalytic action of a platinum catalyst, the dynamic vulcanization of the silicone rubber is carried out through the addition reaction of vinyl in the vinyl silicone rubber and hydrogen-containing silicone oil (Licheng, the preparation of polyurethane/silicone rubber dynamic vulcanization thermoplastic elastomer and the performance research of the Master academic paper of Guangdong university of industry in 2011), the material selects polyester TPU as the base material of TPSiV, the compatibility of the TPU and the silicone rubber is improved through the method of adding a compatilizer, however, the compatibility between TPU and silicone rubber is poor, and the TPSiV prepared by the method has the defect of poor interface compatibility, so that the product is easy to crack at the interface in the bending process, and the service performance of the material is influenced.
Disclosure of Invention
The invention aims to provide a high-bending-resistance dynamic vulcanized silicone rubber/thermoplastic polyurethane elastomer material and a preparation method thereof aiming at the defects and shortcomings in the prior art.
In order to achieve one aspect of the above object, the present invention provides a dynamically vulcanized silicone rubber/thermoplastic polyurethane elastomer material, which adopts the following technical scheme:
a dynamic vulcanized silicone rubber/thermoplastic polyurethane elastomer material comprises the following components in parts by weight:
vinyl polysiloxane: 100 parts of (A);
thermoplastic polyurethane elastomer: 10-300 parts;
10-300 parts of organic silicon modified thermoplastic polyurethane elastomer;
hydrogen-containing silicone oil: 0.1-15 parts; and
a sufficient amount of a platinum group catalyst.
According to the materials of the invention, in the present invention, vinyl polysiloxane is particularly selected as the silicone rubber; preferably, the vinyl polysiloxane is a vinyl polysiloxane having the following general structural formula in order to better bond with the elastomer and improve its properties:
in the formula, R1And R2Alkyl, haloalkyl or aryl of 1 to 10 carbon atoms, which are identical or different, preferably selected from methyl, ethyl, propyl, butyl and trifluoropropyl and phenyl, respectively;
v is vinyl; the vinyl polysiloxane preferably has a vinyl content of 0.04 to 10 mol%, more preferably 0.06 to 9 mol%, even more preferably 0.08 to 8 mol%, such as 1 mol%, 2 mol%, 4 mol% or 6 mol%; the number of vinyl groups in a single vinyl polysiloxane molecule is preferably 2 or more, such as 3 or 4; the viscosity of the vinyl polysiloxane at room temperature is preferably 1000-15000mpa · s, more preferably 2000-13000mpa · s, further preferably 2500-12000mpa · s, such as 4000mpa · s, 6000mpa · s, 8000mpa · s or 10000mpa · s;
m is an integer selected from 80-500, preferably 100-400, further preferably 150-300, such as 200, 250 or 350;
n is an integer selected from 5 to 100, preferably 8 to 80, more preferably 10 to 70, such as 15, 30 or 50.
Researches show that the vinyl polysiloxane is optimized, so that the dispersion of the polysiloxane in the TPU can be effectively improved, the bending performance of the TPU can be improved, and the surface hand feeling of the TPSiV can be improved.
According to the material of the invention, the thermoplastic polyurethane elastomer can be one or more of polyester thermoplastic polyurethane, polyether thermoplastic polyurethane, polycarbonate thermoplastic polyurethane and polycaprolactone thermoplastic polyurethane; preferably, the thermoplastic polyurethane elastomer is present in an amount of 30 to 200 parts by weight, such as 50, 80, 100, 120 or 150 parts by weight.
According to the material of the present invention, preferably, the silicone modified thermoplastic polyurethane elastomer has the following general structural formula:
in the formula, R3Is an aliphatic diisocyanate residue or an aromatic diisocyanate residue, preferably an aromatic diisocyanate residue, more preferably a4, 4' -diphenylmethane diisocyanate residue;
R4is a branched or straight chain diol residue of C2-C6, preferably a branched or straight chain diol residue of C3-C5, more preferably a branched or straight chain diol residue of C4;
R5any one of the structures a1) -a7) described below, wherein,
a1) a linear or branched alkyl residue from C2 to C10;
a2) is-C6H12The person skilled in the art understands that it can likewise be linear or branched;
a3) is-C3H6OC2H4The person skilled in the art understands that it can likewise be linear or branched;
a4) is composed of
wherein-C is understood by those skilled in the art3H6-can likewise be linear or branched;
a5) is composed of
a6) Is composed of
a7) Is composed of
R6And R7Is the same or different alkyl or halogenated alkyl of C1-C18, C6-C18 aromatic hydrocarbon or halogenated aromatic hydrocarbon, preferably methyl or phenyl;
x is an integer from 1 to 30, preferably from 2 to 15, such as 5, 8 or 12;
y is an integer from 1 to 300, preferably from 4 to 150, such as 10, 50 or 100;
a is an integer from 1 to 150, preferably from 10 to 50, such as 5, 20 or 80;
b is an integer from 1 to 100, preferably from 2 to 50, such as 5, 10, 30 or 80.
In the present invention, the "residue" refers to a structural moiety remaining in a monomer in a polymer due to participation of a partial group of the monomer in chemical bond formation.
According to the material of the present invention, preferably, the usage ratio of the silicone modified thermoplastic polyurethane to the thermoplastic polyurethane elastomer is not less than 1:2, such as 1:1, 1.5:1, 2:1 or 3: 1. Because the bonding force of the interface is weak, the material can be cracked in the interface area of the phase in the process of bending and cracking, the compatibility between the TPU substrate of the TPSiV and the silicon rubber is poor, and the bonding force of the two phases is weak, the compatibility between the TPU substrate and the silicon rubber can be better improved by selecting the particularly preferable proportion of the silicon-containing copolymerized TPU (organic silicon modified thermoplastic polyurethane) and the common TPU, the bending resistance of the TPSiV is obviously improved, and the excellent mechanical property of the TPSiV is kept; it is further preferred that the ratio of the sum of the amounts of the silicone-modified thermoplastic polyurethane and the thermoplastic polyurethane elastomer to the amount of silicone rubber is from 1:3 to 3:1, such as from 1:2 to 2:1, such as from 1:1.5, 1:1 or 1.5: 1.
In the present invention, the hydrogen-containing silicone oil is used as a crosslinking agent in an amount of 0.1 to 15 parts, such as 0.5, 1, 5, 10 or 12 parts. According to the material of the present invention, preferably, the hydrogen-containing silicone oil has the following structural general formula:
in the formula, R8Is methyl or hydrogen;
R9is an alkyl group having 1 to 10 carbon atoms, preferably a methyl, ethyl, propyl, isopropyl or butyl group;
c is an integer selected from 5 to 80, preferably 8 to 60, such as 15, 25 or 40;
d is an integer selected from 5 to 100, preferably 10 to 80, such as 20, 40 or 60;
the mass fraction of hydrogen atoms bonded to Si in the hydrogen-containing silicone oil is preferably 0.01 to 1.66%, more preferably 0.05 to 1.6%, and still more preferably 0.08 to 1.58%, such as 1%, 1.2%, or 1.4%; the viscosity at room temperature is preferably 1 to 500 mPas, more preferably 5 to 450 mPas, still more preferably 10 to 400 mPas. It has been found that by optimizing the hydrogen-containing silicone oil, the base material in the material can be better adapted to perform better crosslinking, and the desired mechanical properties can be obtained.
The platinum group catalyst is a sulfided catalyst commonly used in the art, and in the present invention, a sufficient amount of platinum group catalyst means an amount that can achieve the desired degree of crosslinking in the material. Preferably, the platinum group catalyst is used in an amount such that it contains platinum atoms in an amount of 0.5 to 300 parts per million, such as 5 parts per million, 10 parts per million, 50 parts per million, 100 parts per million or 200 parts per million, based on the mass of the vinylpolysiloxane; one or more selected from platinum black, platinum chloride, a mixture of chloroplatinic acid and monohydric alcohol, a complex of chloroplatinic acid and olefin, and platinum acetoacetate; more preferably one or more selected from the group consisting of a mixture of chloroplatinic acid and a monohydric alcohol and a complex of chloroplatinic acid and an olefin; further preferred is a complex of chloroplatinic acid and an olefin.
The material according to the invention may preferably also comprise fillers and/or auxiliaries, such as anti-aging auxiliaries; the filler can be one or more selected from fumed silica, precipitated silica, silicone resin, silica micropowder, diatomite and calcium carbonate; the weight parts of the added filler are preferably 0.1-200 parts, such as 5, 10, 50 or 100 parts; the anti-aging auxiliary agent can be selected from one or more of an antioxidant, an ultraviolet light absorber and a light stabilizer; the anti-aging auxiliary agent is added in an amount of 0.1-5 parts by weight, such as 0.5, 1, 2 or 4 parts by weight.
In order to achieve another aspect of the above objects, the present invention provides a method for preparing the material, comprising the steps of:
(1) high-temperature kneading: fully mixing the other components of the dynamic vulcanization material except the hydrogen-containing silicone oil according to the proportion at the temperature of 150-230 ℃, and then extruding and granulating, such as extruding through a single screw extruder;
(2) dynamic vulcanization: adding the granules obtained by granulation and hydrogen-containing silicone oil into a double-screw extruder according to the proportion, dynamically vulcanizing for 1-8min, such as 2 or 4min, under the conditions that the rotating speed of a main machine is set to 100-1000 r/min, such as 200, 500 or 800 r/min, and the melting temperature is 170-230 ℃, and carrying out granulation and packaging through a granulator device.
Compared with the prior art, the invention has the following beneficial effects:
the invention particularly selects vinyl polysiloxane/thermoplastic polyurethane to carry out dynamic vulcanization to prepare a TPU-based TPSiV product, can obviously improve the bending resistance of the TPSiV, particularly the low-temperature bending resistance, and expand the application field of the TPSiV by optimally adding organic silicon modified thermoplastic polyurethane and hydrogen-containing silicone oil, and the material can be widely applied to the fields of intelligent watches, intelligent watch watchbands and the like with higher requirements on bending resistance, and has remarkable economic and social benefits.
Detailed Description
The present invention is further illustrated below with reference to specific examples, but the scope of the present invention is not limited to these examples. The invention provides a preparation method of a polysiloxane/thermoplastic polyurethane elastomer, which comprises the following steps:
high-temperature kneading: adding organosilicon modified thermoplastic polyurethane, thermoplastic polyurethane elastomer, vinyl silicon polysiloxane, optional inert filler, optional antioxidant, platinum catalyst and antitoxic agent into a kneader at the temperature of 150-200 ℃ for kneading for 1-10min, and extruding and granulating by a single-screw extruder
Dynamic vulcanization: feeding the particles into a double-screw extruder through a weightlessness feeding scale and hydrogen-containing silicone oil through a liquid weightlessness feeding scale, setting the rotating speed of a host machine to be 500 revolutions per minute, dynamically vulcanizing for 1-3min under the conditions that the melting temperature is 170-210 ℃, cutting the particles into finished particles through a granulator device, then injecting the finished particles into a standard test piece through a Haitian SA900 injection molding machine, and carrying out related test representation, wherein the test method comprises the following steps:
hardness testing according to ASTM D4420
Tensile Strength and elongation at Break tested according to ASTM D412
Melt index was measured according to ASTM D1238 under 200 ℃/5kg
Bending resistance was tested according to ASTM D1052
Raw materials and sources used in the examples:
the vinyl polysiloxane is 205-3000 and 205-8000 of Hangzhou Jiande silicone and IOTA3000 of Anhui Eyota silicone oil Co., Ltd, wherein 205-3000 is vinyl polysiloxane with the room temperature viscosity of 3000 centipoises, the vinyl content is 10 mol%, 205-8000 is vinyl polysiloxane with the room temperature viscosity of 8000 centipoises, and the vinyl content is 5 mol%; the IOTA3000 had a room temperature viscosity of 3000 cps and a vinyl content of 0.7 mol%.
Thermoplastic polyurethane elastomer: thermoplastic polyurethane elastomers WHT-1185, WHT-1180 from Vanhua chemical group, Inc., Elastollan-B85A from BASF, and Elastollan-C85A.
The organic silicon modified thermoplastic polyurethane is organic silicon modified polyurethane TSPU20 of Dismann company, the data molecular weight is 80000, and the proportion of organic siloxane is 20% by weight.
The silicone modified polyurethane TSPU35 manufactured by Dismann corporation has a number average molecular weight of 100000. The proportion of the organic siloxane is 35 percent by weight.
The organosilicon modified polyurethane E2-860 of AorTech company has a number average molecular weight of 80000, and the proportion of the organosiloxane is 15% by weight.
The organic silicon modified polyurethane E5-130 of AorTech company has a number average molecular weight of 50000 and the proportion of organic siloxane is 40% by weight.
The hydrogen-containing silicone oil is TNH-0.18 of Tianshuan silicone rubber science and technology Limited company of Guangdong Dongguan city and CG-0.38 of Zhonglan Chenguang, wherein the TNH-0.18 has the room temperature viscosity of 100 centipoises and the mass fraction of hydrogen connected with Si is 0.18 wt%; CG-0.38 viscosity at room temperature is 70 centipoise, and mass fraction of hydrogen bonded to Si is 0.38 wt%.
The catalyst is ACS-Pt-100 of Shanghai Silibao high-new materials and DC4000 of Dow Corning organic silicon, and the main components of the catalyst are complexes of chloroplatinic acid and vinyl polysiloxane.
The inert filler is fumed silica M-5 in the Kabot fine chemical industry, and the antioxidant is antioxidant 1010 in the Bassfer Ciba fine chemical industry.
The formulations of the examples and comparative examples are shown in table 1:
TABLE 1 continuation of the table
Table 2: results of Performance testing
TABLE 2 continuation of the table
Through the analysis of the examples and the comparative examples, it can be seen that the TPSiV prepared by using the organic silicon modified TPU has very beneficial room temperature and low temperature bending resistance, and meanwhile, the material still retains higher physical and mechanical properties.
Claims (27)
1. A dynamic vulcanized silicone rubber/thermoplastic polyurethane elastomer material comprises the following raw material components in parts by weight:
vinyl polysiloxane: 100 parts of (A);
thermoplastic polyurethane elastomer: 30-300 parts;
10-300 parts of organic silicon modified thermoplastic polyurethane elastomer;
hydrogen-containing silicone oil: 0.1-15 parts; and
a sufficient amount of a platinum group catalyst;
wherein the dosage ratio of the organic silicon modified thermoplastic polyurethane to the thermoplastic polyurethane elastomer is not less than 1: 2;
the organic silicon modified thermoplastic polyurethane elastomer has the following structural general formula:
in the formula, R3Is an aliphatic diisocyanate residue or an aromatic diisocyanate residue;
R4a branched or straight chain diol residue from C2 to C6;
R5any one of the structures a1) -a6) described below, wherein,
a1) a linear or branched alkyl residue from C2 to C10;
a2) is-C3H6OC2H4-；
a3) Is composed of
a4) Is composed of
a5) Is composed of
a6) Is composed of
R6And R7Is the same or different C1-C18 alkyl or haloalkyl;
x is an integer from 1 to 30;
y is an integer from 1 to 300;
a is an integer of 1 to 150;
b is an integer of 1 to 100.
2. The material of claim 1, wherein:
the vinyl polysiloxane has the following structural general formula:
in the formula, R1And R2Are the same or different alkyl, haloalkyl or aryl groups having 1 to 10 carbon atoms;
v is vinyl;
m is an integer selected from 80 to 500;
n is an integer selected from 5 to 100.
3. The material of claim 2, wherein: r1And R2Are respectively selected from methyl, ethyl, propyl, butyl, trifluoropropyl and phenyl; m is an integer selected from 100-400; n is an integer selected from 8 to 80.
4. The material of claim 3, wherein: m is an integer selected from 150-300; n is an integer selected from 10 to 70.
5. The material of claim 1 or 2, wherein: the vinyl polysiloxane has a vinyl content of 0.04-10 mol%, a vinyl number in a single molecule of not less than 2, and a viscosity of 1000-.
6. The material of claim 5, wherein: the vinyl polysiloxane has a vinyl content of 0.06-9 mol%, and a viscosity at room temperature of 2000-.
7. The material of claim 6, wherein: the vinyl polysiloxane had a vinyl content of 0.08-8 mol%, a viscosity of 2500 mPa-.
8. A material according to any of claims 1 to 4 and 6 to 7, wherein the thermoplastic polyurethane elastomer is one or more of a polyester thermoplastic polyurethane and a polyether thermoplastic polyurethane;
the weight portion of the thermoplastic polyurethane elastomer is 30-200.
9. The material of claim 1, wherein: r3Is an aromatic diisocyanate residue;
R4a branched or straight chain diol residue from C3 to C5;
R6and R7Is methyl or phenyl;
x is an integer from 2 to 15;
y is an integer from 4 to 150;
a is an integer of 10 to 50
b is an integer of 2 to 50.
10. The material of claim 9, wherein: r3Is a4, 4' -diphenylmethane diisocyanate residue; r4Is a branched or straight chain diol residue of C4.
11. The material of any one of claims 1-4, 6-7, and 9-10, wherein: the ratio of the sum of the usage amount of the organic silicon modified thermoplastic polyurethane and the thermoplastic polyurethane elastomer to the usage amount of the vinyl polysiloxane is 1:3-3: 1.
12. The material of claim 11, wherein: the hydrogen-containing silicone oil has the following structural general formula:
in the formula, R8Is methyl or hydrogen;
R9is an alkyl group having 1 to 10 carbon atoms;
c is an integer selected from 5 to 80 and d is an integer selected from 5 to 100.
13. The material of claim 12, wherein: r9Is methyl, ethyl, propyl or butyl; c is an integer selected from 8 to 60, d isSelected from integers from 10 to 80.
14. A material as claimed in claim 12 or 13, wherein: the hydrogen-containing silicone oil has a mass fraction of Si-bonded hydrogen atoms of 0.01-1.66% and a viscosity at room temperature of 1-500mpa @.
15. The material of claim 14, wherein: the hydrogen-containing silicone oil has a mass fraction of Si-bonded hydrogen atoms of 0.05-1.6% and a viscosity at room temperature of 5-450mpa @.
16. The material of claim 15, wherein: the hydrogen-containing silicone oil has a mass fraction of hydrogen atoms bonded to Si of 0.08-1.58% and a viscosity at room temperature of 10-400mpa ≤.
17. The material of any one of claims 1-4, 6-7, 9-10, 12-13, and 15-16, wherein: the platinum catalyst is used in an amount such that the platinum atom contained therein is in an amount of 0.5 to 300 parts per million by mass of the vinylpolysiloxane.
18. The material of claim 17, wherein: the platinum group catalyst is selected from one or more of platinum black, platinum chloride, a mixture of chloroplatinic acid and monohydric alcohol, a complex of chloroplatinic acid and olefin, and platinum acetoacetate.
19. The material of claim 18, wherein: the platinum group catalyst is selected from one or more of a mixture of chloroplatinic acid and a monohydric alcohol and a complex of chloroplatinic acid and an olefin.
20. The material of claim 19, wherein: the platinum catalyst is a complex of chloroplatinic acid and olefin.
21. The material of any one of claims 1-4, 6-7, 9-10, 12-13, 15-16, and 18-20, wherein: the material also comprises a filler and/or an anti-aging auxiliary agent.
22. The material of claim 21, wherein: the filler is selected from one or more of fumed silica, precipitated silica, silicone resin, silica micropowder, diatomite and calcium carbonate; the anti-aging auxiliary agent is selected from one or more of an antioxidant, an ultraviolet light absorber and a light stabilizer.
23. The material of claim 22, wherein: the weight portion of the added filler is 0.1-200; the weight portion of the added anti-aging auxiliary agent is 0.1-5.
24. The material of claim 1, wherein: r5is-C6H12-。
25. The material of any one of claims 1-4 and 6-7, wherein: the thermoplastic polyurethane elastomer is one or more of polycarbonate thermoplastic polyurethane and polycaprolactone thermoplastic polyurethane;
the weight portion of the thermoplastic polyurethane elastomer is 30-200.
26. The material of claim 12, wherein: r9Is isopropyl; c is an integer selected from 8 to 60 and d is an integer selected from 10 to 80.
27. Method for the preparation of a material according to any one of claims 1-26, comprising the steps of:
(1) high-temperature kneading: fully mixing the other components of the dynamic vulcanization material except the hydrogen-containing silicone oil according to corresponding parts by weight at the temperature of 150-230 ℃, and then extruding and granulating;
(2) dynamic vulcanization: adding the granules obtained by granulation and hydrogen-containing silicone oil into a double-screw extruder according to the proportion, dynamically vulcanizing for 1-8min under the conditions that the rotating speed of a main machine is set to 100-.
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| CN112143231B (en) * | 2020-08-21 | 2022-03-29 | 北京化工大学 | Silicone rubber/polyurethane thermoplastic vulcanized rubber and preparation method and application thereof |
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