CN109485826A - A kind of branched chain type thermoplastic silicone polyurethane elastomer and preparation method thereof - Google Patents
A kind of branched chain type thermoplastic silicone polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN109485826A CN109485826A CN201811340752.7A CN201811340752A CN109485826A CN 109485826 A CN109485826 A CN 109485826A CN 201811340752 A CN201811340752 A CN 201811340752A CN 109485826 A CN109485826 A CN 109485826A
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Abstract
The invention discloses a kind of branched chain type thermoplastic silicone polyurethane elastomers and preparation method thereof, its main feature is that the branched chain type thermoplastic silicone polyurethane is made of diisocyanate, single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen, and it is prepared as follows: I, single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen is uniformly mixed, obtains uniform pre-polymerization mixed liquor；II, at a temperature of 60~120 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, it is mixed uniformly, reacts casting and cure.The branched chain type thermoplastic silicone polyurethane elastomer not only has good physical mechanical property, especially has excellent hydrophobic performance, smooth sense of touch and good resistance to low temperature etc..
Description
Technical field
The invention belongs to elastomeric material fields, further to a kind of branched chain type thermoplastic silicone polyurethane elastomer
And preparation method thereof.
Background technique
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 has good thermal stability, oxidative resistance, and good water repellency, low glass transition temperature is low
Surface energy, excellent physiological inertia.Dimethyl silicone polymer (PDMS) is a kind of most common polysiloxane, and PDMS is drawn
The research for entering to be made siliceous TPU into TPU is more.The existing hand about in the research for preparing siliceous TPU, substantially by being copolymerized
Section introduces PDMS on the main chain of TPU.
As Chinese patent CN104448231A discloses preparation method, the production of a kind of polyether silicones block polyurethane material
Product and purposes, the invention use two-step method, select MDI/BDO as hard section, and soft segment selects polyethylene oxide-polydimethylsiloxanes
The siliceous TPU that molecular backbone contains PDMS is prepared in alkane-polyethylene oxide (PEO-PDMS-PEO).
As Chinese patent CN 106565933A discloses a kind of preparation method of silicone thermoplastic's polyurethane, the invention
Selecting polyester and polyether polyalcohol, two terminal-reactive PDMS, chain extender, diisocyanate is raw material, by it is different feed intake it is suitable
Sequence is prepared for a kind of siliceous TPU material that molecular backbone contains PDMS structure
As United States Patent (USP) US 006313254B1 discloses preparation, the composition of a kind of polyurethane elastomer containing polysiloxanes
And performance, the invention select MDI/BDO as hard section, soft segment at least selects a kind of polysiloxanes macromolecular diol and at least one
A kind of siliceous TPU product that molecular backbone contains PDMS has been prepared in polyethers/polycarbonate macromolecular diol.
Chinese patent CN104086740A discloses a kind of preparation of organosilicon grafted and modified polyurethane resin of use for synthetic leather
Method, what is introduced is a kind of polyether silicone, it is therefore an objective to be obtained usually by the smooth feel of silicon-containing compound bring, high glaze
With the performance lasting holding of coating surface, what is obtained is cross-linked polymer, is unable to thermoplastic processing.
Preparing a kind of branched chain type thermoplastic silicone polyurethane elastomer that molecular side chain contains PDMS structure yet there are no report
Road.
Summary of the invention
The purpose of the present invention is to provide a kind of branched chain type thermoplastic silicone polyurethane elastomer and preparation method thereof, choosings
With the raw material containing single terminal-reactive silicone macromolecule, by the method for copolymerization, a kind of molecular side chain is prepared and contains
The branched chain type thermoplastic silicone polyurethane elastomer of PDMS structure, the branched chain type thermoplastic silicone polyurethane elastomer is not only
With good physical mechanical property, especially there is excellent hydrophobicity, smooth sense of touch and good resistance to low temperature etc..
To reach the above goal of the invention, technical scheme is as follows:
A kind of branched chain type thermoplastic silicone polyurethane elastomer, it is characterised in that the elastomer by following components polymerize and
At, by total weight be 100 parts based on:
Diisocyanate: 20~40 parts, preferably 25~38 parts, more preferable 30~38 parts；
Single terminal-reactive silicone macromolecule: 1~18 part, preferably 2~11 parts, more preferable 4-~8 part；
Other macromolecular compounds containing active hydrogen: 37~72 parts, preferably 44~61 parts, more preferable 50~56 parts；Small point
Sub- chain extender: 3~14 parts, preferably 3~12 parts, more preferable 5~12 parts；
Wherein single terminal-reactive silicone macromolecule refers to that one end of silicone macromolecule is non-reacted group
Sealing end, the other end are the group end capping containing single functionality or polyfunctionality hydroxyl.It is preferred that single terminal-reactive organosilicon divides greatly
Son be strand single end have 2 reactive hydrogens and another end do not have reactive hydrogen straight chain silicone molecules (that is,
Polysiloxane oligomers).It is preferred that elastomer obtained is the comb that main chain is polyurethane segment, side chain is polysiloxanes segment
Shape polymer.
Preferably, in the branched chain type thermoplastic silicone polyurethane elastomer, the list terminal-reactive organosilicon
Macromolecular is any one in molecular structure shown in structural formula I:
The integer that n in structure above I is 1~50, X are following a1)~a10) any one in structure, Q1And Q2
For-CH3、In any one；a1)-C3H6-Y；a2)-C4H8-Y；a3)-C5H10-Y；a4)-C6H12-Y；a5)-
C3H6OC2H4-Y；a6)-C3H6OCH2CH(Y)CH2OCH3；a7)a8)a9)a10)–OH；a11)
a1)~a10) Y in structure be-OH,In any one,
It is preferred that the integer that n is 2~20 in the structural formula I, X is preferably a1)、a3)、a5)、a11) any one in structure
Kind, Y is preferably
Preferably, the branched chain type thermoplastic silicone polyurethane elastomer, it is characterised in that the diisocyanate
For at least one of aliphatic, alicyclic and aromatic diisocyanate, preferably toluene di-isocyanate(TDI), diphenyl methane two
Isocyanates, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, to benzene two
Isocyanates, naphthalene diisocyanate, 1,4- cyclohexane diisocyanate, benzene dimethylene diisocyanate, two methylene of hexamethylene
Group diisocyanate, trimethyl -1,6- hexamethylene diisocyanate, tetramethyl m-xylylene diisocyanate, drop ice
Piece alkane diisocyanate, dimethyl diphenyl diisocyanate, Methylcyclohexyl diisocyanate, dimethyl diphenylmethane two are different
At least one of cyanate, lysine diisocyanate；More preferable toluene di-isocyanate(TDI), diphenylmethane diisocyanate
Ester, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and to benzene diisocyanate
At least one of ester.
Preferably, preferably described (preferably to divide containing active hydrogen in the branched chain type thermoplastic silicone polyurethane elastomer
Subchain end contain active hydrogen) macromolecular compound select molecular structure be HO-R-OH, and average molecular weight be 600~
8000g/mol, preferably average molecular weight are 800-6000g/mol, wherein the structure of R be aliphatic or aromatic polyester, polyethers,
Polycarbonate, polycyclic ester, polylactic acid, any one in polyolefin, appointing preferably in aliphatic or aromatic polyester, polyethers
It anticipates one kind, more preferable polytetrahydrofuran, polypropylene oxide, poly terephthalic acid -1,6- hexylene glycol ester, polyadipate ethylene glycol
Any one in ester, poly adipate succinic acid ester.
Preferably, in the branched chain type thermoplastic silicone polyurethane elastomer, the small molecule chain extender is fat
Race and/or aromatic micromolecule chain extender, preferably ethylene glycol, 1,4-butanediol, diglycol, triethylene-glycol, 1,
2- propylene glycol, neopentyl glycol, methyl propanediol, 1,6-HD, 1,3- propylene glycol, dipropylene glycol, tripropylene glycol,
Butyl ethyl propylene glycol, diethyl pentanediol, 3- methyl-1,5- pentanediol, 1,3 butylene glycol, 1,2- butanediol, 2,3- fourth two
Alcohol, trimethylpentanediol, 1,5- pentanediol, 1,2- pentanediol, hydroxypivalyl hydroxypivalate neopentyl alcohol ester, 2- ethyl -1,3- oneself two
Alcohol, 12 carbon glycol, 1,4- hydroxymethyl-cyclohexane, 1,4- cyclohexanediol, hydroquinone two hydroxy ethyl ether, resorcinol dihydroxy
Ethylether, resorcinol bis-hydroxypropyl ether, resorcinol bis-hydroxypropyl ethylether, 4- ethoxy oxygen ethyl -1- hydroxyethylbenzene two
Ether, 3- ethoxy oxygen ethyl -1- hydroxyethylbenzene diether, bisphenol-A dihydroxyethyl ether, bisphenol-A dihydroxypropyl ether, 1,4- hexamethylene two
At least one of amine, diamino-dicyclohexyl methane, trimethylhexane diamine, dimethyl diamino-dicyclohexyl methane；
It is further preferred that ethylene glycol, 1,4-butanediol, diglycol, 1,6- hexylene glycol, 1,3-PD, a contracting dipropyl
One of glycol, 1,5- pentanediol, 1,4- cyclohexane diamine are a variety of.
Invention additionally provides above-mentioned branched chain type thermoplastic silicone method for preparing polyurethane elastic body, including it is following
Step:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；II, at a temperature of 60~120 DEG C, preferably 70-110 DEG C, by diisocyanate
It is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly, reacts casting and cure.
In the present invention, the branched chain type thermoplastic silicone polyurethane elastomer, it is preferable that raw materials used middle isocyanic acid
The molar ratio of root and active hydrogen is 0.8~1.3:1, more preferable 0.9~1.2:1.
In the present invention, the branched chain type thermoplastic silicone polyurethane elastomer, it is preferable that containing active in the raw material
The molar ratio of other macromolecular compounds of hydrogen and single terminal-reactive silicone macromolecule is 0.2~10:1, more preferable 0.4-
8:1.
Preferably, the branched chain type thermoplastic silicone polyurethane elastomer number-average molecular weight obtained by the present invention is greater than 1.0
×105(such as 1.2 × 105~1.0 × 106), tensile strength is greater than 20MPa, and glass transition temperature is lower than -90 DEG C, Static Water
Contact angle is greater than 110 °.
The positive effect of the present invention is: the present invention obtained by branched chain type thermoplastic silicone polyurethane elastomer in addition to
Outside with good mechanical property, also there is excellent hydrophobic performance, smooth sense of touch and good resistance to low temperature etc..This hair
Bright branched chain type thermoplastic silicone polyurethane elastomer is because have these excellent performances, and can be used for separately made product
It directly uses, is applied to multiple fields, such as footwear material, intelligence wearing, wire and cable.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Range be only limitted to embodiment below.Without departing from the idea of the above method of the present invention, according to the common skill in this field
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
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: methyl diphenylene diisocyanate, 33 parts；
2) single terminal-reactive silicone macromolecule (X-22-2713, Shin-Etsu Chemial Co., Ltd): 6 parts；
Wherein Q1And Q2For-CH3, n 2, X are；
3) other macromolecular compounds containing active hydrogen: poly terephthalic acid -1,6- hexylene glycol esterdiol, average molecular weight
For 1000g/mol, 54 parts；
4) small molecule chain extender: ethylene glycol, 7 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 100 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly
It closes, reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Comparative example 1
The raw material for preparing thermoplastic polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: methyl diphenylene diisocyanate, 33 parts；
2) other macromolecular compounds containing active hydrogen: poly terephthalic acid -1,6- hexylene glycol esterdiol, average molecular weight
For 1000g/mol, 60 parts；
3) small molecule chain extender: ethylene glycol, 7 parts；
Preparation method includes the following steps:
I, other macromolecular compounds, small molecule chain extender containing active hydrogen are uniformly mixed, it is mixed obtains uniform pre-polymerization
Close liquid；
II, at a temperature of 100 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly
It closes, reaction is poured and cures.
The performance parameter of prepared thermoplastic polyurethane elastomer is as shown in table 1.
Comparative example 2
Prepare the raw material of organosilicon grafted and modified polyurethane resin:
1) diisocyanate: toluene di-isocyanate(TDI), 25 parts, methyl diphenylene diisocyanate, 35 parts, toluene；
2) (CoatOSil 3305, Mitugao New Material Group, average molecular weight are single terminal-reactive polyether silicone
50000): 30 parts；
3) polyester-diol: average molecular weight 2000g/mol, 140 parts；
4) small molecule chain extender: 1,4-butanediol, 8 parts, ethylene glycol, 10 parts；
5) solvent: dimethylformamide, 400 parts, toluene, 250 parts, butanone, 100 parts；
Preparation method includes the following steps:
By 110 DEG C of vacuum dehydration 1h of polyester-diol, 50 DEG C are cooled to, sequentially adds dimethylformamide, single end reaction
Property polyether silicone, 1,4-butanediol, ethylene glycol, stir evenly, sequentially add toluene di-isocyanate(TDI), diphenyl methane two
Isocyanates, stirring are warming up to 75 DEG C, react 3.5h, add toluene, are kept for 75 DEG C of temperature, and with two isocyanide of diphenyl methane
Acid esters thickening, is cooled to 60 DEG C, then add butanone and stir evenly after viscosity reaches predetermined value, is cooled to 30 DEG C of dischargings, obtains
The organosilicon grafted and modified polyurethane resin solution that solid content is 25%；
Performance parameter after prepared organosilicon grafted and modified polyurethane resin baking and curing crosslinking is as shown in table 1.
Embodiment 2
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: dicyclohexyl methyl hydride diisocyanate, 25 parts；
2) single terminal-reactive silicone macromolecule (X-22-2489, Shin-Etsu Chemial Co., Ltd): 1 part；
Wherein Q1And Q2For-CH3, n 20, X are
3) other macromolecular compounds containing active hydrogen: poly- carbonic acid -1,6- hexylene glycol esterdiol, average molecular weight are
2500g/mol, 68 parts；
4) small molecule chain extender: diglycol, 6 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 80 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mix it uniformly,
Reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 3
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: isophorone diisocyanate, toluene di-isocyanate(TDI), 40 parts, and two isocyanide of isophorone
The weight ratio of acid esters and toluene di-isocyanate(TDI) is 1:1；
2) single terminal-reactive silicone macromolecule (X-22-3275, Shin-Etsu Chemial Co., Ltd): 18 parts；
Wherein Q1And Q2For-CH3, n 50, X are
3) other macromolecular compounds containing active hydrogen: polytetrahydrofuran diol, average molecular weight 600g/mol, 37
Part；
4) small molecule chain extender: 1,6- hexylene glycol, 5 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 60 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mix it uniformly,
Reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 4
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: benzene dimethylene diisocyanate, 30 parts；
2) single terminal-reactive silicone macromolecule (X-22-2650, Shin-Etsu Chemial Co., Ltd): 8 parts；
Wherein Q1And Q2For-CH3, n 20, X are
3) other macromolecular compounds containing active hydrogen: polytetrahydrofuran diol, average molecular weight 2000g/mol, 50
Part；
4) small molecule chain extender: neopentyl glycol, Isosorbide-5-Nitrae-cyclohexanediol, 12 parts, and neopentyl glycol and Isosorbide-5-Nitrae-cyclohexanediol
Weight ratio is 1:3；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 100 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly
It closes, reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 5
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: toluene di-isocyanate(TDI), 36 parts；
2) single terminal-reactive silicone macromolecule (X-22-3385, Shin-Etsu Chemial Co., Ltd): 14 parts；
Wherein Q1And Q2For-CH3, n 10, X are
3) other macromolecular compounds containing active hydrogen: polytetrahydrofuran diol, average molecular weight 1000g/mol, 47
Part；
4) small molecule chain extender: 1,4-butanediol, 3 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 90 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mix it uniformly,
Reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 6
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: hexamethylene diisocyanate, 20 parts；
2) single terminal-reactive silicone macromolecule (X-22-8739, Shin-Etsu Chemial Co., Ltd): 2 parts；
Wherein Q1And Q2For-CH3, n 1, X are
3) other macromolecular compounds containing active hydrogen: polyoxypropyleneglycol, average molecular weight 8000g/mol, 72
Part；
4) small molecule chain extender: Isosorbide-5-Nitrae-cyclohexane diamine, 6 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 120 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly
It closes, reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 7
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: methyl diphenylene diisocyanate, 32 parts；
2) single terminal-reactive silicone macromolecule (X-22-7593, Shin-Etsu Chemial Co., Ltd): 4 parts；
Wherein Q1And Q2ForN is that 30, X is
3) other macromolecular compounds containing active hydrogen: polytetrahydrofuran diol (average molecular weight 2000g/mol) gathers
Ethylene glycol adipate glycol (average molecular weight 2000g/mol), 56 parts, and polytetrahydrofuran diol and polyadipate second two
The weight ratio of alcohol esterdiol is 1:3；
4) small molecule chain extender: 1,4-butanediol, 8 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 100 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly
It closes, reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 8
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: paraphenylene diisocyanate, 24 parts；
2) single terminal-reactive silicone macromolecule (X-22-5534, Shin-Etsu Chemial Co., Ltd): 11 parts；
Wherein Q1And Q2For-CH3, n 15, X are
3) other macromolecular compounds containing active hydrogen: polyethylene glycol adipate glycol, average molecular weight 2000g/
Mol, 61 parts；
4) small molecule chain extender: 1,5-PD, 4 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 100 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly
It closes, reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 9
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: toluene di-isocyanate(TDI), 23 parts；
2) single terminal-reactive silicone macromolecule (X-22-8346, Shin-Etsu Chemial Co., Ltd): 10 parts；
Wherein Q1And Q2For-CH3, n 20, X are
3) other macromolecular compounds containing active hydrogen: (average molecular weight is poly- carbonic acid -1,6-HD esterdiol
2500g/mol), polycaprolactone glycol (average molecular weight 1500g/mol), 62 parts, and poly- carbonic acid -1,6- hexylene glycol esterdiol
Weight ratio with polycaprolactone glycol is 1:4；
4) small molecule chain extender: neopentyl glycol, 1,3-PD, 5 parts, and the weight ratio of neopentyl glycol and 1,3-PD
For 2:3；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 110 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly
It closes, reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 10
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: naphthalene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 31 parts, and naphthalene diisocyanate with
The weight ratio of 1,4- cyclohexane diisocyanate is 1:2；
2) single terminal-reactive silicone macromolecule (X-22-7925, Shin-Etsu Chemial Co., Ltd): 15 parts；
Wherein Q1And Q2For-CH3, n 30, X are-C4H8OH；
3) other macromolecular compounds containing active hydrogen: polycaprolactone glycol, average molecular weight 1500g/mol, 44 parts；
4) small molecule chain extender: dipropylene glycol, 10 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 110 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mixes it uniformly
It closes, reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 11
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: cyclohexanedimethyleterephthalate diisocyanate, 38 parts；
2) single terminal-reactive silicone macromolecule (X-22-7633, Shin-Etsu Chemial Co., Ltd): 6 parts；
Wherein Q1And Q2For-CH3, n 20, X are
3) other macromolecular compounds containing active hydrogen: (average molecular weight is poly- carbonic acid -1,6-HD esterdiol
2500g/mol), polytetrahydrofuran diol (average molecular weight 2000g/mol), 53 parts, and poly- carbonic acid -1,6- hexylene glycol ester two
The weight ratio of alcohol and polytetrahydrofuran diol is 1:1；
4) small molecule chain extender: 1,3-PD, 1,6- hexylene glycol, 3 parts, and 1,3-PD and 1, the weight of 6- hexylene glycol
Amount is than being 1:2；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 80 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mix it uniformly,
Reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
Embodiment 12
The raw material for preparing branched chain type thermoplastic silicone polyurethane elastomer is based on 100 parts by total weight:
1) diisocyanate: Isosorbide-5-Nitrae-cyclohexane diisocyanate, hexamethylene diisocyanate, 28 parts, and Isosorbide-5-Nitrae-hexamethylene
The weight ratio of alkane diisocyanate and hexamethylene diisocyanate is 1:4；
2) single terminal-reactive silicone macromolecule (X-22-9224, Shin-Etsu Chemial Co., Ltd): 17 parts；
Wherein Q1And Q2For-CH3, n 10, X are
3) other macromolecular compounds containing active hydrogen: polybutylene glyool adipate, average molecular weight 5000g/
Mol, 41 parts；
4) small molecule chain extender: 2- ethyl -1,3- hexylene glycol, 14 parts；
Preparation method includes the following steps:
I, by single terminal-reactive silicone macromolecule, other macromolecular compounds, small molecule chain extender containing active hydrogen
It is uniformly mixed, obtains uniform pre-polymerization mixed liquor；
II, at a temperature of 90 DEG C, diisocyanate is added in pre-polymerization mixed liquor obtained by step I, mix it uniformly,
Reaction is poured and cures.
The performance parameter of prepared branched chain type thermoplastic silicone polyurethane elastomer is as shown in table 1.
1 branched chain type thermoplastic silicone polyurethane elastomer performance of table
As can be seen from the above table, the product of the embodiment of the present invention has good tensile strength, elongation at break, hydrophobicity
The balance of energy, resistance to low temperature.
Claims (9)
1. a kind of branched chain type thermoplastic silicone polyurethane elastomer, it is characterised in that the elastomer by following components polymerize and
At, by total weight be 100 parts based on:
Diisocyanate: 20~40 parts, preferably 25~38 parts；
Single terminal-reactive silicone macromolecule: 1~18 part, preferably 2~11 parts；
Other macromolecular compounds containing active hydrogen: 37~72 parts, preferably 44~61 parts；
Small molecule chain extender: 3~14 parts, preferably 3~12 parts；
Wherein single terminal-reactive silicone macromolecule refers to that one end of silicone macromolecule is non-reacted group end capping,
The other end is the group end capping containing single functionality or polyfunctionality hydroxyl.
2. branched chain type thermoplastic silicone polyurethane elastomer as described in claim 1, it is characterised in that the list end is anti-
Answering property silicone macromolecule is 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)~
a10) any one in structure: a1)-C3H6-Y；a2)-C4H8-Y；a3)-C5H10-Y；a4)-C6H12-Y；a5)-C3H6OC2H4-Y；
a6)-C3H6OCH2CH(Y)CH2OCH3；a7)a8)a9)a10)–OH；a11)
a1)~a10) Y in structure be-OH,In any one,
It is preferred that the integer that n is 2~20 in the structural formula I, X is preferably a1)、a3)、a5)、a11) any one in structure, Y is excellent
It is selected as
3. branched chain type thermoplastic silicone polyurethane elastomer as claimed in claim 1 or 2, it is characterised in that two isocyanide
Acid esters is at least one of aliphatic, alicyclic and aromatic diisocyanate, preferably toluene di-isocyanate(TDI), diphenylmethyl
It is alkane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, right
Phenylene diisocyanate, naphthalene diisocyanate, 1,4- cyclohexane diisocyanate, benzene dimethylene diisocyanate, hexamethylene two
Methylene diisocyanate, trimethyl -1,6- hexamethylene diisocyanate, tetramethyl m-xylylene diisocyanate,
Norbornene alkyl diisocyanate, dimethyl diphenyl diisocyanate, Methylcyclohexyl diisocyanate, dimethyl diphenylmethane
One of diisocyanate, lysine diisocyanate are a variety of；More preferable toluene di-isocyanate(TDI), diphenyl methane two are different
Cyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and different to benzene two
One of cyanate is a variety of.
4. branched chain type thermoplastic silicone polyurethane elastomer as claimed in any one of claims 1-3, it is characterised in that institute
Stating other macromolecular compounds containing active hydrogen and selecting molecular structure is HO-R-OH, and average molecular weight is 600~8000g/
Mol, wherein the structure of R is aliphatic or aromatic polyester, polyethers, polycarbonate, polycyclic ester, polylactic acid, appointing in polyolefin
Anticipate one kind, preferably any one in aliphatic or aromatic polyester, polyethers, more preferable polytetrahydrofuran, polypropylene oxide,
Poly terephthalic acid -1,6-HD ester, polyethylene glycol adipate, any one in poly adipate succinic acid ester.
5. such as branched chain type thermoplastic silicone polyurethane elastomer of any of claims 1-4, it is characterised in that institute
Stating small molecule chain extender is aliphatic and/or aromatic micromolecule chain extender, preferably ethylene glycol, 1,4-butanediol, a contracting diethyl
Glycol, triethylene-glycol, 1,2- propylene glycol, neopentyl glycol, methyl propanediol, 1,6-HD, 1,3- propylene glycol, a contracting two
Propylene glycol, tripropylene glycol, butyl ethyl propylene glycol, diethyl pentanediol, 3- methyl-1,5- pentanediol, 1,3 butylene glycol,
1,2- butanediol, 2,3- butanediol, trimethylpentanediol, 1,5- pentanediol, 1,2- pentanediol, hydroxypivalyl hydroxypivalate neopentyl alcohol
Ester, 2- ethyl -1,3- hexylene glycol, 12 carbon glycol, 1,4- hydroxymethyl-cyclohexane, 1,4- cyclohexanediol, hydroquinone dihydroxy
Ethylether, resorcinol dihydroxyethyl ether, resorcinol bis-hydroxypropyl ether, resorcinol bis-hydroxypropyl ethylether, 4- ethoxy
Oxygen ethyl -1- hydroxyethylbenzene diether, 3- ethoxy oxygen ethyl -1- hydroxyethylbenzene diether, bisphenol-A dihydroxyethyl ether, bisphenol-A dihydroxy
Propyl ether, 1,4- cyclohexane diamine, diamino-dicyclohexyl methane, trimethylhexane diamine, dimethyl diaminocyclohexyl first
One of alkane is a variety of；More preferable ethylene glycol, 1,4- butanediol, diglycol, 1,6-HD, 1,3- propylene glycol,
One of dipropylene glycol, 1,5- pentanediol, 1,4- cyclohexane diamine are a variety of.
6. branched chain type thermoplastic silicone polyurethane elastomer according to any one of claims 1-5, wherein branched chain type
The number-average molecular weight of thermoplastic silicone polyurethane elastomer is greater than 1.0 × 105, tensile strength is greater than 20MPa, glass transition
Temperature is lower than -90 DEG C, and Static water contact angles are greater than 110 °.
7. branched chain type thermoplastic silicone method for preparing polyurethane elastic body described according to claim 1~any one of 6,
Characterized by the following steps:
I, single terminal-reactive silicone macromolecule, other macromolecular compounds containing active hydrogen, small molecule chain extender are mixed
Uniformly, uniform pre-polymerization mixed liquor is obtained；II, at a temperature of 60~120 DEG C, diisocyanate is added to pre- obtained by step I
It in poly- mixed liquor, mixes it uniformly, react casting and cure.
8. preparation method according to claim 7, it is characterised in that: mole of raw materials used middle isocyano and active hydrogen
Than for 0.8~1.3:1.
9. preparation method according to claim 7 or 8, it is characterised in that: other big points in the raw material containing active hydrogen
The molar ratio of sub- compound and single terminal-reactive silicone macromolecule is 0.2~10:1.
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| CN112979962A (en) * | 2021-02-04 | 2021-06-18 | 成都思立可科技有限公司 | Branched-chain type organic silicon modified polyurethane elastomer and preparation method thereof |
| CN112898529A (en) * | 2021-02-07 | 2021-06-04 | 武汉纺织大学 | Asymmetric star-shaped polyurethane thickener with cationic core and preparation method thereof |
| CN112898529B (en) * | 2021-02-07 | 2022-06-07 | 武汉纺织大学 | Asymmetric star-shaped polyurethane thickener with cationic core and preparation method thereof |
| CN114133506A (en) * | 2021-12-14 | 2022-03-04 | 美瑞新材料创新中心(山东)有限公司 | High-resilience flexible biodegradable resin and preparation method and application thereof |
| CN114656614A (en) * | 2022-01-27 | 2022-06-24 | 中国科学院长春应用化学研究所 | Polyurethane elastomer and application thereof |
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