CN117603427A - Organosilicon modified polyurethane with wear-resistant effect, and preparation method and application thereof - Google Patents
Organosilicon modified polyurethane with wear-resistant effect, and preparation method and application thereof Download PDFInfo
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- CN117603427A CN117603427A CN202311293113.0A CN202311293113A CN117603427A CN 117603427 A CN117603427 A CN 117603427A CN 202311293113 A CN202311293113 A CN 202311293113A CN 117603427 A CN117603427 A CN 117603427A
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- Prior art keywords
- modified polyurethane
- silicone
- prepolymer
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000000694 effects Effects 0.000 title abstract description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 23
- 239000004626 polylactic acid Substances 0.000 claims abstract description 23
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920003023 plastic Polymers 0.000 claims abstract description 16
- 239000004033 plastic Substances 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 8
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 229920005903 polyol mixture Polymers 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract 5
- 239000010703 silicon Substances 0.000 claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 13
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 9
- -1 amine compound Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims 2
- 239000000806 elastomer Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- FNAZRRHPUDJQCJ-UHFFFAOYSA-N henicosane Chemical compound CCCCCCCCCCCCCCCCCCCCC FNAZRRHPUDJQCJ-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000004597 plastic additive Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- INAMEDPXUAWNKL-UHFFFAOYSA-N nonadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCN INAMEDPXUAWNKL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
-
- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides organosilicon modified polyurethane with wear-resistant effect, and a preparation method and application thereof, wherein the organosilicon modified polyurethane is obtained by reacting a system comprising the following components: (a) Polyisocyanates having at least two isocyanate groups; (b) A polymer polyol mixture comprising a polylactic acid polyol and a hydroxyl-containing silicone prepolymer; (c) a chain extender; (d) A capping agent having a long carbon chain hydrocarbyl group having at least one isocyanate group reactive group. According to the invention, the organic silicon modified polyurethane with wear resistance, toughness, mechanical property and hand feeling is obtained by introducing the crystalline polylactic acid chain segment, the organic silicon chain segment and the long carbon chain hydrocarbon group into the polyurethane, and the organic silicon modified polyurethane has good compatibility with most plastics, so that the wear resistance, toughness, hydrophobicity and hand feeling of the plastics can be obviously improved by adding the organic silicon modified polyurethane into the plastics.
Description
Technical Field
The invention belongs to the technical field of plastic additive assistants, and particularly relates to organosilicon modified polyurethane with an abrasion-resistant effect, and a preparation method and application thereof.
Background
The wear-resistant agent is a plastic additive capable of improving the wear resistance of the surface of a material, preventing the surface of the material from being scratched, and reducing the friction between materials. The conventional wear-resistant auxiliary agents mainly comprise molybdenum disulfide, graphite, glass fiber, carbon fiber, polytetrafluoroethylene, silicone oil and the like, wherein the molybdenum disulfide is mainly used for increasing the crystallinity of nylon materials and is mainly used for nylon plastics, and the application range is limited; graphite has a unique network structure so that it can slide relative to each other with little friction, but this wear resistance is particularly important in environments where water is present; the glass fiber improves the wear resistance of the thermoplastic plastic through reinforcement, polytetrafluoroethylene and silicone oil can reduce the friction coefficient of the plastic so as to improve the wear resistance of the plastic, but most of inorganic wear-resistant agents such as molybdenum disulfide, graphite, glass fiber and the like can influence the toughness and the handfeel of the plastic, and polytetrafluoroethylene and silicone oil can influence the strength and the mechanical property of the plastic.
Therefore, development of a wear-resistant material with wear resistance, which does not affect toughness and mechanical strength of plastics, is a technical problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide organosilicon modified polyurethane with a wear-resistant effect, a preparation method and application thereof, and the organosilicon modified polyurethane with wear resistance, toughness, mechanical property and hand feeling is obtained by introducing a crystalline polylactic acid chain segment, an organosilicon chain segment and a long carbon chain alkyl into polyurethane, and the organosilicon modified polyurethane has good compatibility with most plastics, and can obviously improve the wear resistance, toughness, hydrophobicity and hand feeling of plastics when being added into plastics.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a silicone-modified polyurethane obtained by reacting a reaction system comprising:
(a) Polyisocyanates having at least two isocyanate groups;
(b) A polymer polyol mixture comprising a polylactic acid polyol and a hydroxyl-containing silicone prepolymer;
(c) A chain extender;
(d) A capping agent having a long carbon chain hydrocarbyl group having at least one isocyanate group reactive group.
Preferably, the molar ratio between isocyanate groups and hydroxyl groups in the reaction system is 1.02-1.2.
Preferably, the mass ratio between the polylactic acid polyol and the hydroxyl-containing organopolysiloxane prepolymer in the component (b) is (5 to 7): (3-5); wherein 5 to 7 can be 5.5, 6, 6.5, etc.; 3 to 5 may be 3.5, 4, 4.5, etc.
Illustratively, the polyisocyanate includes one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 4-tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate trimer, xylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, and the like.
Preferably, the component (d) has a long carbon chain hydrocarbon group of capping agent added in an amount of 1 to 15 parts by weight based on 100 parts by weight of the total weight of the reaction system; for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, and the like can be used.
Preferably, the component (c) chain extender is added in an amount of 1 to 5 parts by weight based on 100 parts by weight of the total weight of the reaction system.
Preferably, the end-capping agent of component (d) having a long carbon chain hydrocarbyl group is a long carbon chain monofunctional amine compound.
Preferably, the end-capping agent of component (d) having a long carbon chain hydrocarbon group comprises an aliphatic primary amine having 15 to 22 carbon atoms; for example, the carbon number may be 16, 17, 18, 19, 20, 21, etc.
The blocking agent having a long carbon chain hydrocarbon group may be one or more of pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, heneicosane, and eicosediamine.
Preferably, the component (d) comprises a dihydroxyl chain extender and/or a trihydric chain extender.
Preferably, the dihydroxyl chain extender comprises one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol and neopentyl glycol.
Preferably, the molecular weight of the polylactic acid polyol is 1000-2000 g/mol.
Preferably, the hydroxyl-containing organopolysiloxane prepolymer comprises a double-ended monohydroxy silicone prepolymer and/or a single-ended dihydroxy silicone prepolymer.
The hydroxyl-containing organopolysiloxane prepolymer described above can be prepared according to methods well known in the art, and commercially available products can also be purchased.
Preferably, the viscosity of the hydroxyl-containing organopolysiloxane prepolymer is 15 to 100cps.
In a second aspect, the present invention provides a method for preparing the above-mentioned silicone modified polyurethane, the method comprising the steps of:
s1, reacting a polyisocyanate with at least two isocyanate groups of a component (a) and a polymer polyol mixture of a component (b) to obtain a prepolymer;
s2, after the prepolymer and the component (c) chain extender are subjected to chain extension reaction, the prepolymer and the component (d) end capping agent are subjected to reaction, and then cooling and crystallization are carried out, so that the organosilicon modified polyurethane is obtained.
Preferably, in the step S1, the temperature of the reaction is 70-80 ℃; the reaction time is 3-5 h;
preferably, the step S1 further includes a catalyst;
preferably, in step S2, the reaction time is 1 to 3 hours.
Preferably, the catalyst includes an organotin catalyst, an organobismuth catalyst, and the like.
Preferably, the catalyst is added in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the total weight of the raw materials in step S1.
Preferably, an appropriate amount of an organic solvent such as acetone, methyl ethyl ketone, butyl acetate, ethyl acetate, toluene, xylene, etc. may be added for dilution according to the actual reaction conditions.
In a third aspect, the invention provides the use of the above-described silicone-modified polyurethane in plastic products.
In a fourth aspect, the invention provides an antiwear agent comprising the silicone modified polyurethane described above or a silicone modified polyurethane prepared according to the preparation method described above.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares the organosilicon modified polyurethane with wear-resistant effect by taking polyisocyanate, polymer polyol mixture (comprising polylactic acid polyol and hydroxyl-containing organosilicon prepolymer), a capping agent with long carbon chain hydrocarbon groups and a chain extender as main preparation raw materials, wherein the organosilicon modified polyurethane has organosilicon chain segments with tendency of enriching surfaces, lower polarity can reduce friction coefficient, and the polylactic acid polyol has excellent crystallinity, and the lubricity brought by the long carbon chain hydrocarbon groups at the tail ends of the chain segments jointly endows the resin with excellent wear resistance. Meanwhile, the organosilicon modified polyurethane with the wear-resistant effect not only has amino acid ester polar groups, but also has long-carbon chain hydrocarbon nonpolar groups, has excellent compatibility with most of high polymer resins, can endow the high polymer resins with excellent wear resistance, toughness and hand feeling, and can be suitable for most of high polymer resin products.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. In the present specification, "part" and "%" respectively mean "part by mass" and "% by mass" unless otherwise specified.
Example 1
The preparation method of the organosilicon modified polyurethane comprises the following steps:
(1) 50g of dehydrated polylactic acid polyol (Fengyuan, PLA 1000), 50g of double-end monohydroxy organosilicon prepolymer (Silok 8812) and 40g of 4,4' -dicyclohexylmethane diisocyanate (HMDI) are put into a reaction kettle with a stirrer, a reflux condenser and a thermometer, and after 0.05g of organobismuth catalyst is added, the temperature is raised to 80 ℃, and the reaction is carried out for 3 hours under heat preservation, thus obtaining prepolymer;
(2) Adding 0.9g of ethylene glycol and 0.6g of trimethylolpropane into the prepolymer, continuously reacting for 2 hours, adding 12g of octadecylamine for end capping, ending the reaction, cooling, and crystallizing to obtain white solid organosilicon modified polyurethane.
Example 2
The preparation method of the organosilicon modified polyurethane comprises the following steps:
(1) 60g of dehydrated polylactic acid polyol (PLA 2000), 40g of double-end monohydroxy organosilicon prepolymer (silok 8812) and 35g of isophorone diisocyanate (IPDI) are put into a reaction kettle with a stirrer, a reflux condenser and a thermometer, and after 0.1g of organic bismuth catalyst is added, the temperature is raised to 75 ℃, and the reaction is carried out for 3.5 hours, thus obtaining prepolymer;
(2) 2.3g of butanediol and 1g of trimethylolpropane are added into the prepolymer, the reaction is continued for 1.5h, 9g of pentadecylamine is added for end capping, the reaction is ended, and the temperature is reduced and crystallization is carried out, so that the white solid organosilicon modified polyurethane is obtained.
Example 3
The preparation method of the organosilicon modified polyurethane comprises the following steps:
(1) 70g of dehydrated polylactic acid polyol (PLA 1000), 30g of double-end monohydroxy organosilicon prepolymer (silok 8812) and 45g of diphenylmethane-4, 4' -diisocyanate (MDI) are put into a reaction kettle with a stirrer, a reflux condenser and a thermometer, 1g of organobismuth catalyst is added, and then the temperature is raised to 80 ℃ and the reaction is kept for 3 hours, thus obtaining prepolymer;
(2) Adding 4g of propylene glycol and 0.5g of glycerol into the prepolymer, continuously reacting for 2 hours, adding 7.5g of nineteen amine for end capping, ending the reaction, cooling and crystallizing to obtain white solid organosilicon modified polyurethane.
Example 4
This embodiment differs from embodiment 1 only in that: n-octadecylamine was replaced with an equivalent molar amount of n-undecylamine.
Example 5
This embodiment differs from embodiment 1 only in that: maintaining the R value (n) in the prepolymer NCO ：n OH ) The mass ratio of polylactic acid polyol (PLA 1000) to double-ended monohydroxy silicone prepolymer (silok 8812) was changed from 50:50 to 10:90 without change.
Example 6
This embodiment differs from embodiment 1 only in that: maintaining the R value (n) in the prepolymer NCO ：n OH ) The mass ratio of polylactic acid polyol (PLA 1000) to double-ended monohydroxy silicone prepolymer (silok 8812) was changed from 50:50 to 90:10 without change.
Comparative example 1
A silicone-modified polyurethane which differs from example 1 in that: maintaining the R value (n) in the prepolymer NCO ：n OH ) The procedure of example 1 was repeated except that the polylactic acid polyol was not added, and the other materials, parameters and steps were the same.
Comparative example 2
A silicone-modified polyurethane which differs from example 1 in that: maintaining the R value (n) in the prepolymer NCO ：n OH ) The same procedure as in example 1 was followed except that the double-ended monohydroxy silicone prepolymer was not added, but the other materials, amounts, parameters and steps were the same.
Comparative example 3
A silicone-modified polyurethane which differs from example 1 in that: the octadecylamine was replaced with an equivalent molar amount of butylamine and the other starting materials, amounts, parameters and procedures were the same as in example 1.
Application examples 1 to 6, comparative application examples 1 to 3
An abrasion resistant TPU comprising 5g of an abrasion resistant agent, 100g of a polyester TPU and 0.5g of an antioxidant 1010.
The abrasion resistant agent was the silicone-modified polyurethane obtained in examples 1 to 6 and comparative examples 1 to 3.
Performance test:
crushing the organosilicon modified polyurethane obtained in examples 1-6 and comparative examples 1-3 to obtain organosilicon modified polyurethane powder, mixing 5g of the organosilicon modified polyurethane powder, 100g of polyester TPU and 0.5g of antioxidant 1010, and extruding, cooling and granulating by a double-screw extruder to obtain a plastic product; the plastic products were sampled and tested according to the following criteria and compared with the blank without addition, the test properties of which are shown in table 1.
(1) Abrasion resistance test: testing was performed according to standard ASTM D5963; and the wear resistance is represented by the wear resistance index of the volume loss in cubic millimeters, the smaller the value of the volume loss is represented by the better wear resistance, and the smaller the value of the wear resistance index is represented by the worse wear resistance.
(2) Tensile strength: testing was performed according to standard ASTM D412.
(3) Elongation rate: testing was performed according to standard ASTM D412.
TABLE 1
From the data in table 1, it can be seen that: the organosilicon modified polyurethane with the wear-resistant effect, which is obtained by the embodiment of the invention, is applied to TPU high polymer materials, can obviously improve the wear resistance of TPU, has good compatibility with the TPU high polymer materials, can obviously improve the wear resistance of TPU when being used as an anti-wear agent, and has less influence on the mechanical property of TPU.
Wherein, when the mass ratio between the polylactic acid polyol and the hydroxyl-containing organopolysiloxane prepolymer in the components is (5-7): (3-5) the silicone-modified polyurethane can obtain the best comprehensive properties.
The applicant states that the present invention describes an organosilicon modified polyurethane with abrasion resistance and a preparation method and application thereof by the above examples, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The organic silicon modified polyurethane is characterized in that the organic silicon modified polyurethane is obtained by reacting a reaction system comprising the following components:
(a) Polyisocyanates having at least two isocyanate groups;
(b) A polymer polyol mixture comprising a polylactic acid polyol and a hydroxyl-containing silicone prepolymer;
(c) A chain extender;
(d) A capping agent having a long carbon chain hydrocarbyl group having at least one isocyanate group reactive group.
2. The silicone-modified polyurethane according to claim 1, wherein the molar ratio between isocyanate groups and hydroxyl groups in the reaction system is 1.02 to 1.2.
3. The silicone-modified polyurethane according to claim 1 or 2, wherein the mass ratio between the polylactic acid polyol and the hydroxyl-containing organopolysiloxane prepolymer in the component (b) is (5 to 7): (3-5).
4. The silicone-modified polyurethane according to claim 1, wherein the component (d) has a long carbon chain hydrocarbon group as a capping agent in an amount of 1 to 15 parts by weight based on 100 parts by weight of the total weight of the reaction system;
preferably, the component (c) chain extender is added in an amount of 1 to 5 parts by weight based on 100 parts by weight of the total weight of the reaction system.
5. The silicone-modified polyurethane of claim 1, wherein the component (d) capping agent having a long carbon chain hydrocarbyl group is a long carbon chain monofunctional amine compound;
preferably, the end-capping agent of component (d) having a long carbon chain hydrocarbon group comprises an aliphatic primary amine having 15 to 22 carbon atoms;
preferably, the component (c) comprises a dihydroxyl chain extender and/or a trihydric chain extender.
6. The silicone-modified polyurethane of claim 1, wherein the polylactic acid polyol has a molecular weight of 1000 to 2000g/mol.
Preferably, the hydroxyl-containing organopolysiloxane prepolymer comprises a double-ended monohydroxy silicone prepolymer and/or a single-ended dihydroxy silicone prepolymer;
preferably, the viscosity of the hydroxyl-containing organopolysiloxane prepolymer is 15 to 100cps.
7. The method for producing a silicone-modified polyurethane according to any one of claims 1 to 6, comprising the steps of:
s1, reacting a polyisocyanate with at least two isocyanate groups of a component (a) and a polymer polyol mixture of a component (b) to obtain a prepolymer;
s2, after the prepolymer and the component (c) chain extender are subjected to chain extension reaction, the prepolymer and the component (d) end capping agent are subjected to reaction, and then cooling and crystallization are carried out, so that the organosilicon modified polyurethane is obtained.
Preferably, in the step S1, the temperature of the reaction is 70-80 ℃; the reaction time is 3-5 h;
preferably, the step S1 further includes a catalyst;
preferably, in step S2, the reaction time is 1 to 3 hours.
8. Use of the silicone-modified polyurethane according to any one of claims 1 to 6 or the silicone-modified polyurethane prepared by the preparation method according to claim 7 in plastic products.
9. An antiwear agent, characterized in that it comprises the silicone-modified polyurethane according to any one of claims 1 to 6 or the silicone-modified polyurethane produced by the production method according to claim 7.
10. A modified TPU comprising a thermoplastic polyurethane elastomer and an antiwear agent comprising the silicone modified polyurethane of any one of claims 1-6 or prepared according to the method of claim 7;
preferably, the modified TPU comprises 100 parts of thermoplastic polyurethane elastomer and 2-15 parts of wear resistant agent based on 100 parts by weight of the modified TPU.
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