CN107903369A - A kind of organic silicon polyurethane process for preparation of thermoplastic elastomer and application thereof - Google Patents
A kind of organic silicon polyurethane process for preparation of thermoplastic elastomer and application thereof Download PDFInfo
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- CN107903369A CN107903369A CN201711187447.4A CN201711187447A CN107903369A CN 107903369 A CN107903369 A CN 107903369A CN 201711187447 A CN201711187447 A CN 201711187447A CN 107903369 A CN107903369 A CN 107903369A
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- diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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Abstract
The present invention discloses a kind of organic silicon polyurethane process for preparation of thermoplastic elastomer, which includes the following steps：Ith, at a temperature of 50~120 DEG C, by the way that macromolecular organosilicon dihydric alcohol, diisocyanate, bulking agent are mixed according to certain mode, reaction obtains isocyanate-terminated performed polymer；IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing.Prepared organic silicon polyurethane thermoplastic elastomer (TPE) is in addition to good mechanical property, also with excellent hydrophobic performance and resistance to low temperature.
Description
Technical field：
The invention belongs to elastomeric material field, further to a kind of system of polysiloxane-polyurethane thermoplastic elastomer (TPE)
Preparation Method.
Background technology：
Thermoplastic polyurethane elastomer (TPU) be it is a kind of by thermodynamically incompatible soft segment and hard section form have it is high-strength
The comprehensive material of the excellent properties such as degree, high tenacity, high resiliency, is widely used in all trades and professions.
Organosilicon is the general name of numerous high-molecular compounds containing element silicon, and wherein polysiloxane application is the widest
General, polysiloxane is low with good heat endurance, oxidative resistance, good water repellency, low glass transition temperature
Surface energy, excellent physiological inertia.Dimethyl silicone polymer (PDMS) is a kind of most common polysiloxane, and PDMS is drawn
Enter the most study that siliceous TPU is made into TPU.But since PDMS polarity is low, solubility parameter is small, the phase with other components
Capacitive is poor, causes the physical mechanical property of obtained siliceous TPU poor.
In the existing research on preparing siliceous TPU, substantially by modified soft segment come improve polysiloxane with it is hard
Compatibility between section, including following two aspects：
First, by adding the higher soft segment of another solubility parameter (generally big point of polyethers, polyester, makrolon etc.
Sub- dihydric alcohol), as 006313254 B1 of United States Patent (USP) US disclose a kind of preparation of the polyurethane elastomer containing polysiloxanes,
Composition and performance, which selects MDI/BDO, and as hard section, soft segment at least selects a kind of polysiloxanes macromolecular diol and at least
A kind of polyethers/makrolon macromolecular diol, the physical mechanical property of products therefrom is general, and the operating procedure of the invention is answered
It is miscellaneous.
Second, by carrying out intramolecular modification (as prepared PEO-PMDS-PEO, PCL-PDMS- to polysiloxane
PCL, introduces the side bases such as chloropropyl, nitrile ethyl in PDMS molecules), as Chinese patent CN104448231A discloses a kind of polyethers
Preparation method, product and the purposes of organic block polyurethane material, the invention use two-step method, select MDI/BDO as hard
Section, soft segment select polyethylene oxide-dimethyl silicone polymer-polyethylene oxide (PEO-PDMS-PEO), the mechanics of products therefrom
Intensity is not high, and the invention is difficult to easily be adjusted according to different compositions, there is certain limitation.
Compatibility between polysiloxane and hard section is improved by modified hard section, reduces the phase point between soft and hard segments
From degree, the physical mechanical property of siliceous TPU has not been reported prepared by lifting.
The content of the invention
It is an object of the invention to provide a kind of polysiloxane-polyurethane process for preparation of thermoplastic elastomer, pass through selection
The bulking agent of special construction changes the characteristic of hard section, and by optimizing preparation process, lifting polysiloxane and hard section
Between compatibility, obtain the polysiloxane-polyurethane thermoplastic elastomer (TPE) product with excellent mechanical performances, and the product is also
With excellent hydrophobic performance and resistance to low temperature.
To reach above goal of the invention, technical scheme is as follows：
A kind of polysiloxane-polyurethane process for preparation of thermoplastic elastomer, includes the following steps：
Ith, at a temperature of 50~120 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to one
Fixed mode is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
As a kind of perferred technical scheme, the hybrid mode described in step I selects any one in the following manner,
Preferred embodiment 3)：
Mode 1) macromolecular organosilicon dihydric alcohol, bulking agent are added gradually in diisocyanate successively；
Mode 2) diisocyanate, bulking agent are added gradually in macromolecular organosilicon dihydric alcohol successively；
Mode 3) first macromolecular organosilicon dihydric alcohol is uniformly mixed with bulking agent, mixture is then added gradually to two
In isocyanates；Change the characteristic of polysiloxane-polyurethane thermoplastic elastic material hard section using this hybrid mode, can be more
The solubility parameter of hard section is reduced to big degree, so as to lift the compatibility between polysiloxane soft segment and hard section, is obtained
Polysiloxane-polyurethane thermoplastic elastomer (TPE) product with excellent mechanical performances.
Mode 4) first macromolecular organosilicon dihydric alcohol is uniformly mixed with bulking agent, mixture is obtained, then by two isocyanides
Acid esters is gradually added into the mixture.
In the present invention, the macromolecular organosilicon dihydric alcohol is hydroxyl alkyl-terminated polysiloxane, and is molecule shown in structural formula I
Any one in structure：
The integer that n in structure above I is 1~50, Q1And Q2For-CH3、In any one；X is following a1~
a9Any one in structure, a1)-C3H6-OH；a2)-C4H8-OH；a3)-C5H10-OH；a4)-C6H12-OH；a5)-C3H6OC2H4-
OH；a6)-C3H6OCH2CH(OH)CH2OCH3；a7)a8)a9)
It is preferred that in the structural formula I n be 2~20 integer, X a1、a3、a5Any one in structure.
In the present invention, the bulking agent selects at least one of following molecular structure, preferably b3、b4、b5、b6、b7In
It is at least one.
b1)HOCH2CH2OCH2CH2OH；b2)HOCH(CH3)CH2OCH2CH(CH3)OH；
b3)
b4)b5)
b6)
b7)
In the present invention, the diisocyanate is aliphatic, at least one of alicyclic or aromatic diisocyanate,
Including toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate, hexa-methylene diisocyanate
Ester, dicyclohexyl methyl hydride diisocyanate, paraphenylene diisocyanate, naphthalene diisocyanate, 1,4- cyclohexane diisocyanates, benzene
Dimethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, trimethyl -1,6- hexamethylene diisocyanates, four
Methylresorcinol dimethylene diisocyanate, norbornene alkyl diisocyanate, dimethyl diphenyl diisocyanate, methylcyclohexyl
At least one of diisocyanate, dimethyl diphenylmethane diisocyanate, lysine diisocyanate, preferably toluene two
Isocyanates, methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl
At least one of methane diisocyanate and paraphenylene diisocyanate.
In the present invention, the small molecule chain extender is ethylene glycol, 1,4-butanediol, 1,2-PD, neopentyl glycol, methyl
Propane diols, 1,6-HD, 1,3- propane diols, butyl ethyl propane diols, diethyl pentanediol, 3- methyl isophthalic acids, 5- pentanediols, 1,
3- butanediols, 1,2- butanediols, 2,3- butanediols, trimethylpentanediol, 1,5- pentanediols, preferably 1,2- pentanediols, second two
At least one of alcohol, 1,4- butanediols, 1,6-HD, 1,3- propane diols, 1,5- pentanediols.
It is described to prepare the raw materials used middle macromolecular organosilicon binary of polysiloxane-polyurethane thermoplastic elastomer (TPE) in the present invention
The mass fraction of alcohol is 42~69wt%, preferably 50~60wt%；The mass fraction of bulking agent is 1~15wt%, preferably 5~
10wt%；The mass fraction of diisocyanate is 10~40wt%, preferably 20~30wt%；The mass fraction of small molecule chain extender
For 3~20wt%, preferably 5~10wt%；Based on raw material total amount.
It is described to prepare the raw materials used middle isocyano of polysiloxane-polyurethane thermoplastic elastomer (TPE) and active hydrogen in the present invention
Molar ratio be 0.8~1.3, preferably 0.9~1.1.
Polysiloxane-polyurethane thermoplastic elastomer (TPE) of the present invention, tensile strength can exceed that 20MPa, elongation at break
More than 500%, there is good mechanical property, in addition Static water contact angles are more than 110 °, and glass transition temperature is less than -90
DEG C, there is excellent hydrophobic performance and resistance to low temperature, can be used as bio-medical material, such as aortic airbag, manually
In heart, conduit and blood vessel.
The positive effect of the present invention is：
1st, by varying the structure of hard section, to improve poly-organosilicon in prepared polysiloxane-polyurethane thermoplastic elastomer (TPE)
Compatibility between oxygen alkane and hard section, and then lift the performance of polysiloxane-polyurethane thermoplastic elastomer (TPE)；
2nd, mainly the structure of hard section, including polarity, symmetry etc. are changed by selecting different types of bulking agent, into
And change the solubility parameter and crystallization behavior of hard section, to reach the compatibility improved between polysiloxane and hard section, subtract
The purpose of phase separation degree between small soft and hard segments；
3rd, prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) also has in addition to good physical mechanical property
There are excellent hydrophobic performance and resistance to low temperature, can be used as bio-medical material.
Specific implementation method：
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following embodiment.Without departing from the idea of the above method of the present invention, according to the common skill in this area
The various replacements or change that art knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Prepare the raw material of polysiloxane-polyurethane thermoplastic elastomer (TPE)：
1) macromolecular organosilicon dihydric alcohol：
Wherein Q1And Q2For-CH3, n 50, X areShin-Etsu Chemial Co., Ltd,
KF6003；
2) bulking agent：
HOCH2CH2OCH2CH2OH
3) diisocyanate：1,4- cyclohexane diisocyanates；
4) small molecule chain extender：Neopentyl glycol, methyl propanediol；
Ith, at a temperature of 50 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to certain side
Formula is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
Hybrid mode described in step I selects mode 1)：Macromolecular organosilicon dihydric alcohol, bulking agent are gradually added successively
Enter into diisocyanate；
The mass fraction of macromolecular organosilicon dihydric alcohol is in the raw material for preparing polysiloxane-polyurethane thermoplastic elastic
69wt%, the mass fraction of bulking agent are 1wt%, and the mass fraction of diisocyanate is 10wt%, the matter of small molecule chain extender
Amount fraction is 20wt%, based on raw material total amount.The molar ratio of isocyano and active hydrogen is 0.8 in raw material, small molecule chain extender
Middle neopentyl glycol and the mass ratio of methyl propanediol are 1:2；
The performance of prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) is as shown in table 1.
Embodiment 2
Prepare the raw material of polysiloxane-polyurethane thermoplastic elastomer (TPE)：
1) macromolecular organosilicon dihydric alcohol：
Wherein Q1And Q2ForN is that 1, X is-C3H6- OH, Shin-Etsu Chemial Co., Ltd, X-22-160AS；
2) bulking agent：
HOCH(CH3)CH2OCH2CH(CH3)OH
3) diisocyanate：Benzene dimethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate；
4) small molecule chain extender：Butyl ethyl propane diols；
Ith, at a temperature of 100 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to certain
Mode is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
Hybrid mode described in step I selects mode 2)：Successively diisocyanate, bulking agent are added gradually to divide greatly
In sub- organosilicon dihydric alcohol；
The mass fraction of macromolecular organosilicon dihydric alcohol is in the raw material for preparing polysiloxane-polyurethane thermoplastic elastic
42wt%, the mass fraction of bulking agent are 15wt%, and the mass fraction of diisocyanate is 40wt%, the matter of small molecule chain extender
Amount fraction is 3wt%, based on raw material total amount.The molar ratio of isocyano and active hydrogen is 1.3 in raw material, benzene in diisocyanate
The mass ratio of dimethylene diisocyanate and cyclohexanedimethyleterephthalate diisocyanate is 1:0.5；
The performance of prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) is as shown in table 1.
Embodiment 3
Prepare the raw material of polysiloxane-polyurethane thermoplastic elastomer (TPE)：
1) macromolecular organosilicon dihydric alcohol：
Wherein Q1And Q2For-CH3, n 25, X are-C4H8- OH, Shin-Etsu Chemial Co., Ltd, KF6002；
2) bulking agent：
Bulking agent 1：HOCH(CH3)CH2OCH2CH(CH3)OH
Bulking agent 2：
French SEPPIC companies, Dianol 320；
3) diisocyanate：Hexamethylene diisocyanate；
4) small molecule chain extender：Ethylene glycol；
Ith, at a temperature of 100 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to certain
Mode is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
Hybrid mode described in step I selects mode 2)：Successively diisocyanate, bulking agent are added gradually to divide greatly
In sub- organosilicon dihydric alcohol；
The mass fraction of macromolecular organosilicon dihydric alcohol is in the raw material for preparing polysiloxane-polyurethane thermoplastic elastic
65wt%, the mass fraction of bulking agent are 10wt%, and the mass fraction of diisocyanate is 20wt%, the matter of small molecule chain extender
Amount fraction is 5wt%, based on raw material total amount.The molar ratio of isocyano and active hydrogen is 1.1 in raw material, bulking agent in bulking agent
1 with the mass ratio of bulking agent 2 is 1:0.4；
The performance of prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) is as shown in table 1.
Embodiment 4
Prepare the raw material of polysiloxane-polyurethane thermoplastic elastomer (TPE)：
1) macromolecular organosilicon dihydric alcohol：
Wherein Q1And Q2For-CH3, n 10, X are-C3H6OC2H4- OH, Shin-Etsu Chemial Co., Ltd, KF6000；
2) bulking agent：
French SEPPIC companies, Dianol 220；
3) diisocyanate：Methyl diphenylene diisocyanate；
4) small molecule chain extender：1,4- butanediols；
Ith, at a temperature of 90 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to certain side
Formula is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
Hybrid mode described in step I selects mode 3)：First macromolecular organosilicon dihydric alcohol is uniformly mixed with bulking agent
Close, then mixture is added gradually in diisocyanate；
The mass fraction of macromolecular organosilicon dihydric alcohol is in the raw material for preparing polysiloxane-polyurethane thermoplastic elastic
55wt%, the mass fraction of bulking agent are 10wt%, and the mass fraction of dicyanate is 25wt%, the quality of small molecule chain extender
Fraction is 10wt%, based on raw material total amount.The molar ratio of isocyano and active hydrogen is 1 in raw material；
The performance of prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) is as shown in table 1.
Comparative example 1
Prepare the raw material of polysiloxane-polyurethane thermoplastic elastomer (TPE)：
1) macromolecular organosilicon dihydric alcohol：
Wherein Q1And Q2For-CH3, n 10, X are-C3H6OC2H4- OH, Shin-Etsu Chemial Co., Ltd, KF6000；
2) diisocyanate：Methyl diphenylene diisocyanate；
3) small molecule chain extender：1,4- butanediols；
Ith, at a temperature of 90 DEG C, by the way that macromolecular organosilicon dihydric alcohol, diisocyanate are carried out according to certain mode
Mixing, reaction obtain isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
Hybrid mode described in step I is：Macromolecular organosilicon dihydric alcohol is added gradually in diisocyanate；
The mass fraction of macromolecular organosilicon dihydric alcohol is in the raw material for preparing polysiloxane-polyurethane thermoplastic elastic
55wt%, the mass fraction of dicyanate is 25wt%, and the mass fraction of small molecule chain extender is 20wt%, total based on raw material
Amount.The molar ratio of isocyano and active hydrogen is 1 in raw material；
The performance of prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) is as shown in table 1.
Embodiment 5
Prepare the raw material of polysiloxane-polyurethane thermoplastic elastomer (TPE)：
1) macromolecular organosilicon dihydric alcohol：
Wherein Q1And Q2For-CH3, n 2, X are-C3H6OCH2CH(OH)CH2OCH3, Shin-Etsu Chemial Co., Ltd, X-
22-4952；
2) bulking agent：
BASF AG, HPN；
3) diisocyanate：Toluene di-isocyanate(TDI), hexamethylene diisocyanate；
4) small molecule chain extender：Ethylene glycol, 1,6-HD；
Ith, at a temperature of 120 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to certain
Mode is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
Hybrid mode described in step I selects mode 4)：First macromolecular organosilicon dihydric alcohol is uniformly mixed with bulking agent
Close, obtain mixture, then diisocyanate is gradually added into the mixture；
The mass fraction of macromolecular organosilicon dihydric alcohol is in the raw material for preparing polysiloxane-polyurethane thermoplastic elastic
60wt%, the mass fraction of bulking agent are 5wt%, and the mass fraction of dicyanate is 30wt%, the quality of small molecule chain extender
Fraction is 5wt%, based on raw material total amount.The molar ratio of isocyano and active hydrogen is 1.1 in raw material, toluene in diisocyanate
The mass ratio of diisocyanate and hexamethylene diisocyanate is 1:1, ethylene glycol and 1,6- hexylene glycol in small molecule chain extender
Mass ratio be 1:4；
The performance of prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) is as shown in table 1.
Embodiment 6
Prepare the raw material of polysiloxane-polyurethane thermoplastic elastomer (TPE)：
1) macromolecular organosilicon dihydric alcohol：
Wherein Q1And Q2For-CH3, n 20, X are-C3H6OC2H4- OH, Shin-Etsu Chemial Co., Ltd, KF6001；
2) bulking agent：
INDSPEC chemical companies, TG-210；
3) diisocyanate：Cyclohexanedimethyleterephthalate diisocyanate, hexamethylene diisocyanate；
4) small molecule chain extender：Neopentyl glycol, 1,4- butanediols；
Ith, at a temperature of 100 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to certain
Mode is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
Hybrid mode described in step I selects mode 3)：First macromolecular organosilicon dihydric alcohol is uniformly mixed with bulking agent
Close, then mixture is added gradually in diisocyanate；
The mass fraction of macromolecular organosilicon dihydric alcohol is in the raw material for preparing polysiloxane-polyurethane thermoplastic elastic
62wt%, the mass fraction of bulking agent are 8wt%, and the mass fraction of dicyanate is 20wt%, the quality of small molecule chain extender
Fraction is 10wt%, based on raw material total amount.The molar ratio of isocyano and active hydrogen is 1 in raw material, hexamethylene in diisocyanate
The mass ratio of alkane dimethylene diisocyanate and hexamethylene diisocyanate is 1:2, neopentyl glycol in small molecule chain extender
Mass ratio with 1,4- butanediols is 1:3；
The performance of prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) is as shown in table 1.
Embodiment 7
Prepare the raw material of polysiloxane-polyurethane thermoplastic elastomer (TPE)：
1) macromolecular organosilicon dihydric alcohol：
Wherein Q1And Q2For-CH3, n 10, X are-C3H6OC2H4- OH Shin-Etsu Chemial Co., Ltd, KF6000；
2) bulking agent：
Bulking agent 1：
Arch companies, Poly-G；
Bulking agent 2：
French SEPPIC companies, Dianol 320；
3) diisocyanate：Methyl diphenylene diisocyanate；
4) small molecule chain extender：1,6-HD；
Ith, at a temperature of 80 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to certain side
Formula is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, to obtain the final product
To polysiloxane-polyurethane thermoplastic elastomer (TPE)；
Hybrid mode described in step I selects mode 3)：First macromolecular organosilicon dihydric alcohol is uniformly mixed with bulking agent
Close, then mixture is added gradually in diisocyanate；
The mass fraction of macromolecular organosilicon dihydric alcohol is in the raw material for preparing polysiloxane-polyurethane thermoplastic elastic
52wt%, the mass fraction of bulking agent are 10wt%, and the mass fraction of dicyanate is 30wt%, the quality of small molecule chain extender
Fraction is 8wt%, based on raw material total amount.The molar ratio of isocyano and active hydrogen is 1 in raw material, in bulking agent bulking agent 1 with
The mass ratio of bulking agent 2 is 1:2；
The performance of prepared polysiloxane-polyurethane thermoplastic elastomer (TPE) is as shown in table 1.
1 polysiloxane-polyurethane thermoplastic elastomer (TPE) performance of table
It can be seen that by comparative example 1 and the contrast of embodiment：The mechanical property of embodiment has than comparative example 1 significantly to be carried
Rise, particularly embodiment 4, its mechanical property can reach the rank of general TPU, in addition prepared polysiloxane-polyurethane thermoplastic
Property elastomer also has excellent lower temperature resistance and hydrophobicity.
Claims (10)
1. a kind of polysiloxane-polyurethane process for preparation of thermoplastic elastomer, it is characterised in that include the following steps：
Ith, at a temperature of 50~120 DEG C, by by macromolecular organosilicon dihydric alcohol, bulking agent, diisocyanate according to certain
Mode is mixed, and reaction obtains isocyanate-terminated performed polymer；
IIth, performed polymer obtained by step I is uniformly mixed with small molecule chain extender, and mixture is poured into a mould into post curing, that is, had
Machine silicon-polyurethane termoplastic elastomer.
2. preparation method according to claim 1, it is characterised in that the hybrid mode described in step I is selected with lower section
Any one in formula, preferred embodiment 3)：
Mode 1) macromolecular organosilicon dihydric alcohol, bulking agent are added gradually in diisocyanate successively；
Mode 2) diisocyanate, bulking agent are added gradually in macromolecular organosilicon dihydric alcohol successively；
Mode 3) first macromolecular organosilicon dihydric alcohol is uniformly mixed with bulking agent, mixture is then added gradually to two isocyanides
In acid esters；
Mode 4) first macromolecular organosilicon dihydric alcohol is uniformly mixed with bulking agent, mixture is obtained, then by diisocyanate
It is gradually added into the mixture.
3. preparation method as claimed in claim 1 or 2, it is characterised in that：The macromolecular organosilicon dihydric alcohol is end hydroxyl hydrocarbon
Based polysiloxane, and be any one in molecular structure shown in structural formula I：
The integer that n in structure above I is 1~50, Q1And Q2For-CH3、In any one；X is following a1~a9Knot
Any one in structure, a1)-C3H6-OH；a2)-C4H8-OH；a3)-C5H10-OH；a4)-C6H12-OH；a5)-C3H6OC2H4-OH；
a6)-C3H6OCH2CH(OH)CH2OCH3；a7)a8)a9)
It is preferred that in the structural formula I n be 2~20 integer, X a1、a3、a5Any one in structure.
4. such as the preparation method any one of claim 1-3, it is characterised in that：The bulking agent selects following molecule knot
At least one of structure, preferably b3、b4、b5、b6、b7At least one of：
b1)HOCH2CH2OCH2CH2OH；b2)HOCH(CH3)CH2OCH2CH(CH3)OH；b3)b4)b5)b6)
b7)
5. such as the preparation method any one of claim 1-4, it is characterised in that：The diisocyanate for aliphatic,
At least one of alicyclic or aromatic diisocyanate, preferably toluene di-isocyanate(TDI), methyl diphenylene diisocyanate,
Isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, paraphenylene diisocyanate,
Naphthalene diisocyanate, 1,4- cyclohexane diisocyanates, benzene dimethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate
Ester, trimethyl -1,6- hexamethylene diisocyanates, tetramethyl m-xylylene diisocyanate, two isocyanide of norbornane
Acid esters, dimethyl diphenyl diisocyanate, Methylcyclohexyl diisocyanate, dimethyl diphenylmethane diisocyanate, rely
At least one of propylhomoserin diisocyanate, preferably toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone two
At least one in isocyanates, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and paraphenylene diisocyanate
Kind.
6. such as the preparation method any one of claim 1-5, it is characterised in that：The small molecule chain extender is second two
Alcohol, 1,4- butanediols, 1,2- propane diols, neopentyl glycol, methyl propanediol, 1,6-HD, 1,3- propane diols, butyl ethyl third
Glycol, diethyl pentanediol, 3- methyl isophthalic acids, 5- pentanediols, 1,3 butylene glycol, 1,2- butanediols, 2,3- butanediols, trimethyl penta
One or more in glycol, 1,5- pentanediols, 1,2- pentanediols；Preferably ethylene glycol, 1,4- butanediols, 1,6-HD,
It is one or more in 1,3- propane diols, 1,5- pentanediols.
7. such as the preparation method any one of claim 1-6, it is characterised in that：It is described to prepare polysiloxane-polyurethane heat
The mass fraction of the raw materials used middle macromolecular organosilicon dihydric alcohol of thermoplastic elastic is 42~69wt%, preferably 50~60wt%；
The mass fraction of bulking agent is 1~15wt%, preferably 5~10wt%；The mass fraction of diisocyanate is 10~40wt%, excellent
Select 20~30wt%；The mass fraction of small molecule chain extender is 3~20wt%, preferably 5~10wt%；Based on raw material total amount.
8. such as the preparation method any one of claim 1-7, it is characterised in that：It is described to prepare polysiloxane-polyurethane heat
The molar ratio of the raw materials used middle isocyano of thermoplastic elastic and active hydrogen is 0.8~1.3, preferably 0.9~1.1.
9. a kind of polysiloxane-polyurethane thermoplastic elastomer (TPE) as any one of claim 1-8 is used as bio-medical material
The purposes of material.
10. purposes as claimed in claim 9, the polysiloxane-polyurethane thermoplastic elastomer (TPE) be used for aortic airbag,
In artificial heart, conduit and blood vessel.
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| CN109438646A (en) * | 2018-10-29 | 2019-03-08 | 中海油能源发展股份有限公司 | Polyurethane elastomeric compositions, polyurethane elastomer and preparation method thereof |
| CN109517131A (en) * | 2018-11-12 | 2019-03-26 | 万华化学集团股份有限公司 | Thermoplastic silicone polyurethane and its synthetic method |
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| CN116041651A (en) * | 2022-12-15 | 2023-05-02 | 中国石油大学(北京) | Organosilicon polymer for thickening carbon dioxide, preparation method and application thereof |
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