CN116253889A - Multi-group modified polysiloxane, preparation method and application thereof, and polyurethane foam - Google Patents
Multi-group modified polysiloxane, preparation method and application thereof, and polyurethane foam Download PDFInfo
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- CN116253889A CN116253889A CN202310205834.5A CN202310205834A CN116253889A CN 116253889 A CN116253889 A CN 116253889A CN 202310205834 A CN202310205834 A CN 202310205834A CN 116253889 A CN116253889 A CN 116253889A
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- -1 polysiloxane Polymers 0.000 title claims abstract description 125
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 26
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 62
- 150000003077 polyols Chemical class 0.000 claims abstract description 62
- 229920000570 polyether Polymers 0.000 claims abstract description 56
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 55
- 239000006260 foam Substances 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 25
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 23
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 22
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 3
- 101150065749 Churc1 gene Proteins 0.000 claims description 3
- 102100038239 Protein Churchill Human genes 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- BAVMXDNHWGQCSR-UHFFFAOYSA-N 1-[2-(2,3-dimethylphenyl)ethyl]-2,3-dimethylbenzene Chemical group CC1=CC=CC(CCC=2C(=C(C)C=CC=2)C)=C1C BAVMXDNHWGQCSR-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 11
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003208 petroleum Substances 0.000 abstract description 6
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 5
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000011493 spray foam Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use 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; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
- C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses multi-group modified polysiloxane, a preparation method and application thereof and polyurethane foam, and relates to the technical field of polyurethane rigid foam. The multi-group modified polysiloxane is prepared by adding monoallyl polyoxyethylene ether and a modifier with double ends containing carbon-carbon double bonds to carry out multi-group modification on the basis of polyether modification on low-hydrogen polysiloxane by conventional allyl polyether, so that the problems of coarse cells, high heat conductivity coefficient and the like caused by partial substitution of the bio-based polyol for petroleum-based polyether polyol can be obviously solved, the adding amount of the bio-based polyol can be increased under the condition of the same application effect, and the multi-group modified polysiloxane can be widely applied to the preparation of polyurethane foam as a foam stabilizer under the condition of the same bio-based polyol content.
Description
Technical Field
The invention relates to the technical field of polyurethane rigid foam, in particular to multi-group modified polysiloxane, a preparation method and application thereof and polyurethane foam.
Background
Polyurethane rigid foam is widely used in the fields of household appliances, pipeline heat preservation, refrigerated containers, buildings and the like due to the characteristics of low density, low heat conductivity coefficient and the like. In the prior art, polyurethane rigid foams consist of white and black materials. The main component of the white material is polyether polyol, most of which is from petrochemical or coal chemical products, is non-renewable resource, and the price is limited by energy price fluctuation. Bio-based as a renewable resource is increasingly being studied in terms of polyol preparation, and researchers have developed a variety of bio-based polyols.
CN201510660909.4 reports a bio-based polyurethane spray foam. The high-content bio-based material is applied to heat preservation and water prevention spraying of a wall surface or a roof, so that the foam material has similar performance to the foam produced by all petroleum-based materials; CN201810136827.3 reports a bio-based polyurethane containing carbonate structures. The invention has the characteristics of water resistance, heat resistance and the like, and the preparation method is simple and has low cost.
However, in the process of applying the bio-based polyol to polyurethane foam instead of the conventional polyether polyol, researchers have found some problems of the bio-based polyol, such as darkening of polyurethane foam, coarsening of polyurethane foam surface pore size, reduction of heat conductivity, increase of heat conductivity coefficient, and the like, and even cracking of the foam. At present, bio-based polyols cannot be completely used for replacing petrochemical-based polyethers, and can only be used in a mixed mode or be called as partial replacement.
The application is specifically proposed for improving the situation that a series of problems such as coarsening of cells, rising of heat conductivity coefficient and the like occur in the process of partially replacing petrochemical-based polyether by the bio-based polyol.
Disclosure of Invention
The invention aims to provide multi-group modified polysiloxane, a preparation method and application thereof and polyurethane foam.
The invention is realized in the following way:
in a first aspect, the present invention provides a multi-radical modified polysiloxane having the structural formula
Wherein: m=10 to 60, n=1 to 10, r=1 to 4, p=1 to 3;
R 1 selected from methyl, R 2 、R 3 And R is 4 Any one of them;
R 2 has the general formula of-CH 2 CH 2 CH 2 O(C 2 H 4 O) a (C 3 H 6 O) b R 6 Wherein a=2 to 30, b=2 to 15, r 6 Is H or alkyl containing 1-4 carbon atoms;
R 3 has the general formula of-CH 2 CH 2 CH 2 O(C 2 H 4 O) c H, wherein c=3 to 20;
R 4 the general formula of the catalyst is- (CH) 2 ) x R(CH 2 ) x -or- (CH) 2 ) x R(CH 2 ) x-2 CHCH 2 X=2 to 4, wherein R has the structure: -C w H 2w -, w=1 to 5, or
or-O (C) 2 H 4 O) d (C 3 H 6 O) e -，d＝0～8，e＝0～5，d+e>0 or->
t＝0～15；
R 5 Selected from methyl, R 2 、R 3 And R is 4 Any one of the following.
In a second aspect, the present invention provides a process for the preparation of a multi-group modified polysiloxane according to any one of the preceding embodiments, comprising: the catalyst is prepared by reacting a mixture of a compound containing a carbon-carbon double bond, low-hydrogen polysiloxane, an amine auxiliary agent and a solvent under the action of a catalyst.
In a third aspect, the present invention provides the use of a multi-group modified polysiloxane as described in any of the preceding embodiments or as a foam stabilizer in the preparation of polyurethane foam prepared by the method of preparing a multi-group modified polysiloxane as described in any of the preceding embodiments.
In a fourth aspect, the present invention provides a polyurethane foam comprising a polyether polyol, a bio-based polyol and a foam stabilizer, the mass percent of the polyether polyol and the bio-based polyol being from 50% to 90%:10% -50% of a foam stabilizer, wherein the addition amount of the foam stabilizer is 1% -3% of the total amount of the polyether polyol and the bio-based polyol, and the foam stabilizer is the multi-group modified polysiloxane prepared by any one of the above embodiments or the preparation method of the multi-group modified polysiloxane.
The invention has the following beneficial effects:
the multi-group modified polysiloxane provided by the invention is prepared by adding monoallyl polyoxyethylene ether and a modified substance with double ends containing carbon-carbon double bonds to carry out multi-group modification on the basis of polyether modification of conventional allyl polyether on low-hydrogen polysiloxane. The multi-group modified polysiloxane of the application brings more plasticity in structure, and corresponding groups in the structure can be adjusted according to different types of bio-based polyols. The modified polysiloxane can obviously improve the problems of coarse cells, high heat conductivity coefficient and the like caused by the partial replacement of petroleum-based polyol by the bio-based polyol, can improve the adding amount of the bio-based polyol under the condition of the same application effect, and has better application performance under the condition of the same bio-based polyol content. The multi-group modified polysiloxane provided by the invention is widely applied to the preparation of polyurethane foam as a foam stabilizer, and the problems of coarsening of cells, rising of heat conductivity coefficient and the like caused by the partial substitution of petrochemical polyol by biological polyol in the polyurethane foam added with the multi-group modified polysiloxane are well improved, and the conditions of reduced closed cell rate, parallel compression strength and vertical compression strength are all improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a multi-group modified polysiloxane, which has the structural formula as follows
Wherein: m=10 to 60, n=1 to 10, r=1 to 4, p=1 to 3;
R 1 selected from methyl, R 2 、R 3 And R is 4 Any one of them;
R 2 has the general formula of-CH 2 CH 2 CH 2 O(C 2 H 4 O) a (C 3 H 6 O) b R 6 Wherein a=2 to 30, b=2 to 15, r 6 Is H or alkyl containing 1-4 carbon atoms;
R 3 has the general formula of-CH 2 CH 2 CH 2 O(C 2 H 4 O) c H, wherein c=3 to 20;
R 4 the general formula of the catalyst is- (CH) 2 ) x R(CH 2 ) x -or- (CH) 2 ) x R(CH 2 ) x-2 CHCH 2 X=2 to 4, wherein R has the structure: -C w H 2w -, w=1 to 5, or
or-O (C) 2 H 4 O) d (C 3 H 6 O) e -，d＝0～8，e＝0～5，d+e>0 or->
t＝0～15；
R 5 Selected from methyl, R 2 、R 3 And R is 4 Any one of the following.
Preferably, R 4 The structural formula of (2) is expressed as follows:
wherein->
By M E And (3) representing.
Further, the invention also provides a preparation method of the multi-group modified polysiloxane, which comprises the following steps:
(1) A low hydrogen polysiloxane is prepared.
The low-hydrogen polysiloxane can be purchased commercially or prepared autonomously, and the preparation method comprises the following steps: the low-hydrogen polysiloxane is prepared by taking hexamethyldisiloxane, octamethyl cyclotetrasiloxane and high-hydrogen polysiloxane as raw materials and reacting at 60 ℃ for 8 hours under the condition of an acid catalyst. Wherein the acid catalyst is acid clay.
In the application, the low-hydrogen polysiloxane with different types can be obtained by adjusting the dosage proportion of raw materials of hexamethyldisiloxane, octamethyl cyclotetrasiloxane and high-hydrogen polysiloxane, and can be MD 40 D’ 5 M、MD 35 D’ 7 M、MD 50 D’ 8 M, wherein, the dosage proportion of raw materials of hexamethyldisiloxane, octamethyl cyclotetrasiloxane and high hydrogen polysiloxane is adjusted according to specific types of low hydrogen polysiloxane is a conventional technology, and the application is not specifically described.
(2) Preparing a compound containing a carbon-carbon double bond.
The compound having a carbon-carbon double bond includes allyl polyether, monoallyl polyoxyethylene ether, and a compound having a carbon-carbon double bond at both ends.
Wherein, the allyl polyether realizes polyether modification of polysiloxane, and the average molecular weight of the allyl polyether is 1000-1500; the allyl polyether contains 60-80 mol% of ethoxyl groups, and the tail end of the ethoxyl groups is hydroxyl or methyl.
The monoallyl polyoxyethylene ether has an average molecular weight of 200 to 400;
the modified substance with double ends containing carbon-carbon double bonds comprises at least one of diallyl polyether, polysiloxane with double ends containing carbon-carbon double bonds, terminal diene and bisphenol A diallyl ether polyether; preferably, the polysiloxane having carbon-carbon double bonds at both ends is a vinyl-terminated polydimethylsiloxane. The vinyl-terminated polydimethylsiloxane can be purchased commercially or self-made, and the preparation method comprises the steps of adding octamethyl cyclotetrasiloxane and tetramethyl divinyl disiloxane into a reactor, reacting for 5 hours at 70 ℃ under the action of acid clay to obtain the vinyl-terminated polydimethylsiloxane, and obtaining the vinyl-terminated polydimethylsiloxane with different types by adjusting the dosage proportion of the octamethyl cyclotetrasiloxane and the tetramethyl divinyl disiloxane serving as raw materials, for example, the vinyl-terminated polydimethylsiloxane can be M E D 10 M E 、M E D 8 M E Wherein, the adjustment of the dosage proportion of the vinyl-terminated polydimethylsiloxane to the raw materials according to specific types is a conventional technology, and the application is not specifically described.
Preferably, the mass ratio of allyl polyether, monoallyl polyoxyethylene ether and compound having double carbon-carbon double bond at both ends is 200-250:4-9:1-3.
(3) The catalyst is prepared by reacting a mixture of a compound containing a carbon-carbon double bond, low-hydrogen polysiloxane, an amine auxiliary agent and a solvent under the action of a catalyst.
Specifically, the mass ratio of the compound containing carbon-carbon double bonds, the low-hydrogen polysiloxane and the solvent is 205-262:50-90: feeding 40-50; the dosage of the amine auxiliary agent accounts for 80-120ppm of the total feeding amount; uniformly mixing the compound containing carbon-carbon double bond, low-hydrogen polysiloxane, amine auxiliary agent and solvent to obtain a mixture, stirring the mixture in a nitrogen atmosphere, heating to 85-105 ℃, preserving heat for 0.5-1h, adding a catalyst (the concentration of the catalyst accounting for the weight percent of the total feeding amount is 8-12 ppm), and removing the residual solvent in the mixture after preserving heat for 5-7 h.
Preferably, the amine adjuvant comprises at least one of N, N-dimethylethanolamine, N-dibutylethanolamine, 3-dimethylpropylamine and 2-butylaminoethanol; more preferably, the amine adjuvant is NN-dimethylethanolamine; the solvent is isopropanol or toluene. The catalyst is a palladium-containing complex, a rhodium-containing complex or a platinum-containing complex; more preferably, the catalyst is chloroplatinic acid.
In the application, on the basis of polyether modification of conventional allyl polyether on low-hydrogen polysiloxane, monoallyl polyoxyethylene ether and a modified substance with double end groups containing carbon-carbon double bonds are added for multi-group modification. The multi-group modified polysiloxane of the application brings more plasticity in structure, and corresponding groups in the structure can be adjusted according to different types of bio-based polyols. The modified polysiloxane can obviously improve the problems of coarse cells, high heat conductivity coefficient and the like caused by the partial replacement of petroleum-based polyol by the bio-based polyol, can improve the adding amount of the bio-based polyol under the condition of the same application effect, and has better application performance under the condition of the same bio-based polyol content. The invention is widely applicable to industries such as household appliances, plates and the like.
In addition, the application also provides application of the multi-group modified polysiloxane in preparing polyurethane foam as a foam stabilizer. The multi-group modified polysiloxane can be particularly applied to polyurethane foam with the bio-based polyol partially replacing petrochemical-based polyether as a foam stabilizer, and can solve a series of problems of coarsening of cells, rising of heat conductivity coefficient and the like caused by the fact that the bio-based polyol partially replaces the petrochemical-based polyether.
For example, the present application correspondingly provides a polyurethane foam comprising a petroleum-based polyether polyol, a bio-based polyol and a foam stabilizer, the mass percent of the polyether polyol and the bio-based polyol being 50-90%:10% -50% of foam stabilizer, wherein the addition amount of the foam stabilizer is 1% -3% of the total amount of petroleum-based polyether polyol and bio-based polyol, and the foam stabilizer is the multi-group modified polysiloxane.
The polyurethane foam added with the multi-group modified polysiloxane has the advantages that the problems of coarsening of cells, rising of heat conductivity coefficient and the like caused by the partial substitution of petrochemical polyether by the biological polyol are well improved, and the conditions of reduced closed cell rate, parallel compression strength and vertical compression strength are improved. Under the condition of the same application effect, the adding amount of the bio-based polyol can be increased, and the application performance is better under the condition of the same bio-based polyol content.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a multi-group modified polysiloxane, and the preparation method comprises the following steps: into a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenser were charged 210.0g of an allyl starting polyether having an average molecular weight of 1000 containing 80% by mole of ethyleneoxy groups ending with hydroxyl groups, 9.0g of monoallyl polyoxyethylene ether having an average molecular weight of 400, 1.0g of 1, 8-nonadiene, 90.0g of a low hydrogen polysiloxane (MD 40 D’ 5 M), 50g of isopropanol, 100ppm of N, N-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 85-90 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, preserving heat for 6h, removing the solvent, and obtaining clear and transparent light brown liquid, namely the multi-group modified polysiloxane.
Example 2
The embodiment provides a multi-group modified polysiloxane, and the preparation method comprises the following steps: into a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenser was charged 250.0g of an allyl starting polyether having an average molecular weight of 1500 containing 60 mole percent of ethyleneoxy groups ending in hydroxyl groups, 4.0g of monoallyl polyoxyethylene ether having an average molecular weight of 200, 1.0g of 1, 7-octadiene, 50.0g of a low hydrogen polysiloxane (MD 35 D’ 7 M), 50g of isopropanol, 100ppm of N, N-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 85-90 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, preserving heat for 6h, removing the solvent, and obtaining clear and transparent lightBrown liquid, namely the multi-group modified polysiloxane.
Example 3
The embodiment provides a multi-group modified polysiloxane, and the preparation method comprises the following steps: into a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenser were charged 210.0g of an allyl starting polyether having an average molecular weight of 1000 containing 80 mole percent of ethyleneoxy groups ending with methyl groups, 4.0g of monoallyl polyoxyethylene ether having an average molecular weight of 200, 2.0g of bisphenol A bis allyl ether, 90.0g of a low hydrogen polysiloxane (MD 40 D’ 5 M), 50g of isopropanol, 100ppm of N, N-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 85-90 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, preserving heat for 6h, removing the solvent, and obtaining clear and transparent light brown liquid, namely the multi-group modified polysiloxane.
Example 4
The embodiment provides a multi-group modified polysiloxane, and the preparation method comprises the following steps: 220.0g of an allyl starting polyether having an average molecular weight of 1000 which contains 80% by mole of ethyleneoxy groups and ends with hydroxyl groups, 8.0g of a monoallyl polyoxyethylene ether having an average molecular weight of 400, 3.0g of a diallyl polyether having an average molecular weight of 400 which contains 80% by mole of ethyleneoxy groups, and 80.0g of the resulting low hydrogen polysiloxane (MD 50 D’ 8 M), 40g of toluene, 100ppm of N, N-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 85-90 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, preserving heat for 6h, removing the solvent, and obtaining clear and transparent light brown liquid, namely the multi-group modified polysiloxane.
Example 5
The embodiment provides a multi-group modified polysiloxane, and the preparation method comprises the following steps: 200.0g of an allyl starting polyether having an average molecular weight of 1000 (this polyether contains 80% by mole of ethylene) were charged to a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenserOxy groups, hydroxyl groups at the end), 8.0g monoallyl polyoxyethylene ether having an average molecular weight of 400, 3.0g vinyl-terminated polydimethylsiloxane (M) E D 10 M E ) 80.0g of low-hydrogen polysiloxane (MD) 40 D’ 5 M), 40g of toluene, 100ppm of N, N-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 100-110 ℃, preserving heat for 1h, adding 10ppm chloroplatinic acid, preserving heat for 6h, removing the solvent, and obtaining clear and transparent light brown liquid, namely the multi-group modified polysiloxane.
Example 6
The embodiment provides a multi-group modified polysiloxane, and the preparation method comprises the following steps: into a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenser were charged 240.0g of an allyl starting polyether having an average molecular weight of 1200 containing 80 mol% of ethyleneoxy groups ending with hydroxyl groups, 8.0g of monoallyl polyoxyethylene ether having an average molecular weight of 200, 2.0g of terminal vinyl polydimethylsiloxane (M) E D 8 M E ) 50.0g of the resulting low-hydrogen polysiloxane (MD) 35 D’ 7 M), 40g of toluene, 100ppm of N, N-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 100-110 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, preserving heat for 6h, removing the solvent, and obtaining clear and transparent light brown liquid, namely the multi-group modified polysiloxane.
Comparative example 1
This comparative example provides a modified polysiloxane, which was prepared in substantially the same manner as in example 1, except that: part of the raw materials in example 1 were omitted: 9.0g of monoallyl polyoxyethylene ether having an average molecular weight of 400, 1.0g of 1, 8-nonadiene and 50g of isopropanol.
The preparation method comprises the following steps: into a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenser, was charged 210.0g of an allyl starting polyether having an average molecular weight of 1000 containing 80% by mole of ethyleneoxy groups ending in hydroxyl groups, 90.0g of a low hydrogen polysiloxane (MD 40 D’ 5 M), 100ppm of n, n-dimethylethanolamine. The mixture was put under nitrogenStirring in atmosphere, heating to 85-90 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, preserving heat for 6h to obtain clear and transparent light brown liquid, namely the modified polysiloxane.
Comparative example 2
This comparative example provides a modified polysiloxane, which was prepared in substantially the same manner as in example 2, except that: part of the raw materials in example 2 were omitted: 4.0g of monoallyl polyoxyethylene ether having an average molecular weight of 200, 1.0g of 1, 7-octadiene and 50g of isopropanol.
The preparation method comprises the following steps: into a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenser was charged 250.0g of an allyl starting polyether having an average molecular weight of 1500 containing 60 mole percent of ethyleneoxy groups ending in hydroxyl groups, 50.0g of a low hydrogen polysiloxane (MD 35 D’ 7 M), 100ppm of n, n-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 85-90 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, and preserving heat for 6h to obtain clear and transparent light brown liquid, namely the modified polysiloxane.
Comparative example 3
This comparative example provides a modified polysiloxane, which was prepared in substantially the same manner as in example 3, except that: part of the raw materials in example 3 were omitted: 4.0g of monoallyl polyoxyethylene ether having an average molecular weight of 200, 2.0g of bisphenol A bis allyl ether, 50g of isopropanol.
The preparation method comprises the following steps: into a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenser, was charged 210.0g of an allyl starting polyether having an average molecular weight of 1000 containing 80% by mole of ethyleneoxy groups ending in methyl groups, 90.0g of a low hydrogen polysiloxane (MD 40 D’ 5 M), 100ppm of n, n-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 85-90 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, preserving heat for 6h, removing the solvent, and obtaining clear and transparent light brown liquid, namely the multi-group modified polysiloxane.
Comparative example 4
This comparative example provides a modified polysiloxane, which was prepared in substantially the same manner as in example 4, except that: 8.0g of monoallyl polyoxyethylene ether having an average molecular weight of 400 and 3.0g of a bisallyl polyether having an average molecular weight of 400, which polyether contains 80 mol% of ethyleneoxy groups, were omitted in example 4, while 40g of toluene as a solvent was also omitted.
The preparation method comprises the following steps: 220.0g of an allyl starting polyether having an average molecular weight of 1000 which contains 80% by mole of ethyleneoxy groups and terminal hydroxyl groups and 80.0g of the resulting low hydrogen polysiloxane (MD) 50 D’ 8 M), 100ppm of n, n-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 85-90 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, and preserving heat for 6h to obtain clear and transparent light brown liquid, namely the modified polysiloxane.
Comparative example 5
This comparative example provides a modified polysiloxane, which was prepared in substantially the same manner as in example 6, except that: part of the raw materials in example 6 were omitted: 8.0g of monoallyl polyoxyethylene ether having an average molecular weight of 200, 2.0g of terminal vinyl polydimethylsiloxane (M) E D 8 M E ) 40g of toluene.
The preparation method comprises the following steps: the preparation method comprises the following steps: to a round-bottomed flask equipped with a mechanical stirrer, dry nitrogen line and reflux condenser was added 240.0g of an allyl starting polyether having an average molecular weight of 1200 containing 80% by mole of ethyleneoxy groups ending in hydroxyl groups, 50.0g of a low hydrogen polysiloxane (MD 35 D’ 7 M), 100ppm of n, n-dimethylethanolamine. Stirring the mixture in nitrogen atmosphere, heating to 100-115 ℃, preserving heat for 0.5h, adding 10ppm chloroplatinic acid, and preserving heat for 6h to obtain clear and transparent light brown liquid, namely the modified polysiloxane.
The application evaluation was performed on the examples and comparative examples, and the polyurethane whites were mixed according to the following table, and the application evaluation was compared.
TABLE 1 polyurethane white ingredient parameters (mass ratio)
| Raw materials | Proportion 1 | Proportion 2 | Proportion 3 |
| Polyether polyol A | 100 | 70 | 50 |
| Bio-based polyol B | 0 | 30 | 50 |
| Foam stabilizer | 2.0 | 2.0 | 2.0 |
Polyether polyol A is sucrose-initiated polyether polyol with a hydroxyl number of 380mgKOH/g and a hydroxyl functionality of 6;
the bio-based polyol B is epoxidized soybean oil-based vegetable oil polyol with a hydroxyl value of 310mgKOH/g and a hydroxyl functionality of 4.5.
The performance test is carried out on the obtained rigid polyurethane foam, wherein the measurement of the heat conductivity coefficient refers to the measurement of steady-state thermal resistance and related characteristics of a heat insulation material of GB/T10295-2008, the measurement of the closed pore rate refers to the measurement of the open pore and closed pore volume percentage of the rigid foam of GB/T10799-2008, the test of the compression strength of the rigid polyurethane foam refers to the compression test method of the rigid foam of GB 8813-88, wherein the parallel compression strength refers to the direction parallel to the growth direction of the pressure and the foam, and the vertical compression strength refers to the direction perpendicular to the growth direction of the pressure and the foam.
Table 2 ratio 1 results of test for application Properties of preparation of rigid polyurethane foam
Table 3 results of test on application Properties of rigid polyurethane foam prepared in proportion 2
Table 4 results of test on application Properties of rigid polyurethane foam prepared in proportion 3
As can be seen from table 2, the properties of the respective rigid polyurethane foams are not very different without using bio-based polyols. Tables 3 and 4 show that the conventional modified polysiloxanes have obvious differences in foam properties and increase thermal conductivity as can be seen from the performance test results of each rigid polyurethane foam after the bio-based polyol is added; the closed porosity is reduced; the cell distribution was uneven, and it was shown that the difference between the parallel compressive strength and the perpendicular compressive strength became large. Comparing the data of examples 1-6 and comparative examples 1-5 in tables 3 and 4, it can be seen that the thermal conductivity increases in examples 1-6 are much smaller than in comparative examples 1-5, and the thermal conductivity decreases as the thermal conductivity increases. Meanwhile, the decrease in the closed cell rate in examples 1 to 6 was much smaller than in comparative examples 1 to 5, and the change in the difference between the parallel compressive strength and the perpendicular compressive strength in examples 1 to 6 was much smaller than in comparative examples 1 to 5. The data show that the multi-group modified polysiloxane can obviously improve the addition of the bio-based polyol under the condition of the same application effect, and has better application performance under the condition of the same bio-based polyol content.
In summary, the multi-group modified polysiloxane provided by the application is prepared by adding monoallyl polyoxyethylene ether and a modified substance with double end groups containing carbon-carbon double bonds to carry out multi-group modification on the basis of polyether modification on low-hydrogen polysiloxane by conventional allyl polyether, and monoallyl polyoxyethylene ether and dienyl substances are contained in the molecule of the obtained multi-group modified polysiloxane. The multi-group modified polysiloxane of the application brings more plasticity in structure, and corresponding groups in the structure can be adjusted according to different types of bio-based polyols. The modified polysiloxane can obviously improve the problems of coarse cells, high heat conductivity coefficient and the like caused by the partial replacement of petroleum-based polyol by the bio-based polyol, can improve the adding amount of the bio-based polyol under the condition of the same application effect, and has better application performance under the condition of the same bio-based polyol content. The invention is widely applicable to industries such as household appliances, plates and the like.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A multi-group modified polysiloxane, characterized by the structural formula:
wherein: m=10 to 60, n=1 to 10, r=1 to 4, p=1 to 3;
R 1 selected from methyl, R 2 、R 3 And R is 4 Any one of them;
R 2 has the general formula of-CH 2 CH 2 CH 2 O(C 2 H 4 O) a (C 3 H 6 O) b R 6 Wherein a=2 to 30, b=2 to 15, r 6 Is H or alkyl containing 1-4 carbon atoms;
R 3 has the general formula of-CH 2 CH 2 CH 2 O(C 2 H 4 O) c H, wherein c=3 to 20;
R 4 the general formula of the catalyst is- (CH) 2 ) x R(CH 2 ) x -or- (CH) 2 ) x R(CH 2 ) x-2 CHCH 2 X=2 to 4, wherein R has the structure: -C w H 2w -, w=1 to 5, or
or-O (C) 2 H 4 O) d (C 3 H 6 O) e -，d＝0～8，e＝0～5，d+e>0 or->
t＝0～15；
R 5 Selected from methyl, R 2 、R 3 And R is 4 Any one of the following.
2. The multi-group modified polysiloxane according to claim 1, wherein said R 4 Is expressed as
3. A process for the preparation of a multi-radical modified polysiloxane according to any one of claims 1 to 2, comprising: the catalyst is prepared by reacting a mixture of a compound containing a carbon-carbon double bond, low-hydrogen polysiloxane, an amine auxiliary agent and a solvent under the action of a catalyst.
4. The method for producing a multi-group-modified polysiloxane according to claim 3, wherein the mass ratio of the compound having a carbon-carbon double bond, the low-hydrogen-containing polysiloxane, and the solvent is 205 to 262:50-90:40-50 parts;
preferably, the dosage of the amine auxiliary agent accounts for 80-120ppm of the total feeding amount;
preferably, the catalyst is used in a concentration of 8-12ppm in parts by weight based on the total feed;
preferably, the reaction of the mixture with the catalyst comprises: stirring the mixture in nitrogen atmosphere, heating to 85-105 ℃, preserving heat for 0.5-1h, adding the catalyst, preserving heat for 5-7h, and removing the residual solvent in the mixture.
5. The method for producing a multi-group-modified polysiloxane according to claim 4, wherein the compound having a carbon-carbon double bond comprises allyl polyether, monoallyl polyoxyethylene ether, a compound having a carbon-carbon double bond at both ends;
preferably, the mass ratio of the allyl-containing polyether, the monoallyl polyoxyethylene ether and the compound having a carbon-carbon double bond at both ends is 200 to 250:4-9:1-3.
6. The method for preparing a multi-group modified polysiloxane according to claim 5, wherein the average molecular weight of the allyl-containing polyether is 1000-1500, and the allyl-containing polyether contains 60-80 mol% of ethoxylene groups and hydroxyl groups or methyl groups are at the end.
7. The method for preparing a multi-group modified polysiloxane according to claim 5, wherein the monoallyl polyoxyethylene ether has an average molecular weight of 200 to 400;
preferably, the modifier containing carbon-carbon double bonds at both ends comprises at least one of terminal bis allyl polyether, polysiloxane containing carbon-carbon double bonds at both ends, terminal bis olefin and bisphenol A bis allyl ether;
preferably, the polysiloxane having carbon-carbon double bonds at both ends is a terminal vinyl polydimethylsiloxane.
8. The method for preparing a multi-group modified polysiloxane according to claim 3, wherein the catalyst is a palladium-containing complex, a rhodium-containing complex or a platinum-containing complex; more preferably, the catalyst is chloroplatinic acid;
preferably, the amine auxiliary comprises at least one of N, N-dimethylethanolamine, N-dibutylethanolamine, 3-dimethylpropylamine and 2-butylaminoethanol; more preferably, the amine adjuvant is NN-dimethylethanolamine;
preferably, the solvent is isopropanol or toluene.
9. Use of a multi-group modified polysiloxane according to any one of claims 1 to 2 or a multi-group modified polysiloxane prepared by a method for preparing a multi-group modified polysiloxane according to any one of claims 3 to 8 as a foam stabilizer in the preparation of polyurethane foam.
10. A polyurethane foam, characterized in that it comprises a polyether polyol, a bio-based polyol and a foam stabilizer, wherein the mass percentage of the polyether polyol and the bio-based polyol is 50-90%:10% -50%, the addition amount of the foam stabilizer is 1% -3% of the total amount of the polyether polyol and the bio-based polyol, and the foam stabilizer is the multi-group modified polysiloxane prepared by the preparation method of the multi-group modified polysiloxane according to any one of claims 1-2 or 3-8.
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