CN114716959A - Polyurethane hot melt adhesive for automobile spare tire cover plate and preparation method thereof - Google Patents
Polyurethane hot melt adhesive for automobile spare tire cover plate and preparation method thereof Download PDFInfo
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- CN114716959A CN114716959A CN202111599242.3A CN202111599242A CN114716959A CN 114716959 A CN114716959 A CN 114716959A CN 202111599242 A CN202111599242 A CN 202111599242A CN 114716959 A CN114716959 A CN 114716959A
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- Prior art keywords
- hot melt
- melt adhesive
- hydroxyl
- polyurethane hot
- polymer
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 73
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 56
- 239000004814 polyurethane Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 64
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 57
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 29
- 229920001634 Copolyester Polymers 0.000 claims abstract description 27
- -1 aromatic isocyanate compound Chemical class 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000098 polyolefin Polymers 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000012948 isocyanate Substances 0.000 claims abstract description 17
- 239000000080 wetting agent Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- FBYUNLMTXMFAQK-UHFFFAOYSA-N butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCC.CCCCCCCCCCCC(=O)OCCCC FBYUNLMTXMFAQK-UHFFFAOYSA-N 0.000 claims 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000012975 dibutyltin dilaurate Substances 0.000 description 17
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 17
- 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 14
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229920005604 random copolymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000001164 aluminium sulphate Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000011225 shan shi Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of C09J hot melt adhesives, and particularly provides a polyurethane hot melt adhesive for an automobile spare tire cover plate and a preparation method thereof. The raw materials for preparing the polyurethane hot melt adhesive provided by the invention comprise a polymer with a hydroxyl end group, a crystalline alcohol modified copolyester, a polymer containing hydroxyl and alkoxy, an aromatic isocyanate compound, amine and derivatives thereof, an organic tin compound, random copolymerization polyolefin, an acrylic tackifier, a defoaming agent and an organic silicon wetting agent.
Description
Technical Field
The invention relates to the technical field of C09J hot melt adhesives, and particularly provides a polyurethane hot melt adhesive for an automobile spare tire cover plate and a preparation method thereof.
Background
The automobile spare tire cover plate is an important product in a plurality of products processed by automobile parts, and plays a role in protecting an automobile spare tire and fixing automobile trunk articles. The automobile spare tire cover plate is generally manufactured by hot-pressing a glass fiber polypropylene composite plate coated with an adhesive and a felt. However, in the process, the time difference of 0.5-1 hour exists between the coating adhesive and the hot pressing process, the adhesive is required to be activated for the second time in the actual preparation process, the hot melt adhesive in the prior art is cured before hot pressing, so that the bonding effect between the felt and the polypropylene plate is poor, the phenomenon of edge warping and rebounding of the felt surface is easy to occur, the yield of the automobile spare tire cover plate is low, and the service life is short.
Chinese patent with patent publication No. CN111100592A discloses a latent type single-component polyurethane hot melt adhesive and a preparation method thereof, wherein a closed isocyanate curing agent is added into a polyurethane resin matrix in the disclosure, so that the problems of harsh storage conditions and long curing time of the polyurethane hot melt adhesive in the prior art are solved, but the polyurethane hot melt adhesive prepared by the scheme has strict requirements on the thickness of a coating in the actual use process, the bonding effect of the hot melt adhesive is unstable, and the actual use range of the latent type single-component polyurethane hot melt adhesive is limited;
chinese patent with patent publication No. CN107987779A discloses a reactive polyurethane hot melt adhesive and a preparation method thereof, wherein in the disclosure, specific polyether polyol is used to interact with tackifying resin and filler in a system, so that the water permeability of the hot melt adhesive before curing is improved, and the prepared polyurethane hot melt adhesive has excellent high temperature resistance and thixotropy and is widely applied in the field of hot melt adhesives for vehicle lamps, but the initial strength and the final strength of the hot melt adhesive obtained by the scheme are not reflected obviously.
Therefore, the polyurethane hot melt adhesive provided by the invention has strong controllability of curing time and speed, can realize secondary activation of the polyurethane hot melt adhesive in the preparation process of the automobile spare tire cover plate, and has excellent initial strength, final strength and weather resistance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyurethane hot melt adhesive for an automobile spare tire cover plate, which comprises the following preparation raw materials in percentage by weight: 5-10% of polymer with hydroxyl as end group, 10-20% of crystalline alcohol modified copolyester, 40-60% of polymer containing hydroxyl and alkoxy, 10-20% of aromatic isocyanate compound, 0.1-1% of amine and derivatives thereof, 0.002-0.006% of organic tin compound, 5-10% of random copolymerized polyolefin, 0.1-0.3% of defoaming agent, 0.4-0.6% of organic silicon wetting agent and the balance of acrylic tackifier.
As a preferred embodiment of the present invention, the hydroxyl value of the polymer with hydroxyl as the terminal group is 20-40mg KOH/g.
As a more preferable embodiment of the present invention, the hydroxyl value of the polymer having hydroxyl as a terminal group is 27 to 34mg KOH/g.
In a preferred embodiment of the present invention, the polymer having a hydroxyl group as a terminal group is a polymer obtained by polycondensation of at least one of a monoacid, a diacid, a monoalcohol and a diol.
In a more preferred embodiment of the present invention, the polymer having a hydroxyl group as a terminal group is a polymer obtained by polycondensation of a dibasic acid and a diol.
In a preferred embodiment of the present invention, the dibasic acid includes at least one of oxalic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid.
In a preferred embodiment of the present invention, the diol includes at least one of 1, 2-ethanediol, 1, 4-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, diethylene glycol, and neopentyl glycol.
As a preferred embodiment of the present invention, the number average molecular weight of the crystalline alcohol-modified copolyester is 2500-4500.
In a more preferred embodiment of the present invention, the number average molecular weight of the crystalline alcohol-modified copolyester is 3500.
As a preferred embodiment of the present invention, the viscosity of the hydroxyl-and alkoxy-containing polymer is 100-600cps at 25 ℃.
As a more preferred embodiment of the present invention, the viscosity of the hydroxyl-and alkoxy-containing polymer is 200-400cps at 25 ℃.
As a preferred embodiment of the present invention, the weight average molecular weight of the hydroxyl-and alkoxy-containing polymer is 500-3000.
As a more preferred embodiment of the present invention, the weight average molecular weight of the hydroxyl-and alkoxy-containing polymer is 1000-2500.
As a most preferred embodiment of the present invention, the weight average molecular weight of the hydroxyl-and alkoxy-containing polymer is 2000.
As a preferred technical scheme of the invention, the weight ratio of the polymer with the hydroxyl end group, the crystalline alcohol modified copolyester and the polymer containing the hydroxyl and the alkoxy is 1; (1-3): (4-8).
As a more preferable embodiment of the present invention, the weight ratio of the polymer having a hydroxyl group as a terminal group, the crystalline alcohol-modified copolyester, and the polymer having a hydroxyl group and an alkoxy group is 1; 2: 7.
the applicants have found that when a hydroxyl terminated polymer having a hydroxyl number of from 27 to 34mg KOH/g, a crystalline alcohol-modified copolyester having a number average molecular weight of 3500, a hydroxyl and alkoxy containing polymer having a viscosity of 200-400cps at 25 ℃ are used, especially when the weight ratio of the hydroxyl terminated polymer, the crystalline alcohol-modified copolyester, the hydroxyl and alkoxy containing polymer is 1; 2: 7, polar groups with specific density are introduced into the system, and can react with diphenylmethane diisocyanate in the system, so that the distribution of the polar groups in a soft section and a hard section in a polyurethane molecular chain is improved, the cross-linking density in a hot melt adhesive system is improved, the polarity of the surface of an interface region of the polyurethane hot melt adhesive system is also improved, the bonding force between the polyurethane hot melt adhesive and a glass fiber polypropylene composite plate and felt is enhanced, the initial peeling strength, the final peeling strength and the weather resistance of the hot melt adhesive are improved, the requirement of secondary activation on strength in the preparation process of the hot melt adhesive when the hot melt adhesive is used for preparing the automobile spare tire cover plate is met, the service life of the automobile spare tire cover plate is prolonged, and the problem that the felt surface in the automobile spare tire cover plate is prone to rebound and edge warping is effectively solved.
In a preferred embodiment of the present invention, the aromatic isocyanate compound includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and trimethylbenzene methane triisocyanate.
In a more preferred embodiment of the present invention, the aromatic isocyanate compound is diphenylmethane diisocyanate.
As a preferred technical solution of the present invention, the amine and the derivative thereof include at least one of dimorpholinodiethylether, N-methyldiethanolamine, and triethylenediamine.
As a preferable technical scheme of the invention, the amine and the derivative thereof are dimorpholinodiethylether.
As a preferable technical scheme of the invention, the organic tin compound comprises at least one of dibutyltin dilaurate and stannous octoate.
In a more preferable embodiment of the present invention, the organotin compound is dibutyltin dilaurate.
The applicant unexpectedly finds that when dimorpholinodiethyl ether and dibutyltin dilaurate are added into a system, and the weight percentage of dimorpholinodiethyl ether is controlled to be 0.5%, and the weight percentage of dibutyltin dilaurate is controlled to be 0.004%, the dimorpholinodiethyl ether, the dibutyltin dilaurate and a random copolymerization polyolefin and propionic acid tackifier in the system can cooperate with each other, so that the controllability of the curing time of the polyurethane hot melt adhesive is remarkably improved while the excellent weather resistance of the polyurethane hot melt adhesive is ensured, the polyurethane hot melt adhesive is cured at a low curing speed or not cured before 2 hours and is cured quickly after 2 hours, the requirement of secondary activation within 2 hours of the hot melt adhesive is met, and the yield and the service life of a spare tire cover plate of an automobile are improved.
As a preferable technical scheme of the invention, the melt viscosity of the random copolymerized polyolefin at 190 ℃ is 6000-10000 mPa.s.
In a preferred embodiment of the present invention, the melt viscosity of the random copolymerized polyolefin at 190 ℃ is 8000 mpa.s.
As a preferable embodiment of the present invention, the viscosity of the acrylic tackifier is 100-500mPa.s in a 40% by mass toluene solution at 25 ℃.
As a more preferable technical scheme of the invention, the viscosity of the acrylic tackifier at 25 ℃ and 40% mass concentration in a toluene solution is 250-340 mPa.s.
In a preferred embodiment of the present invention, the defoaming agent includes at least one of polydimethylsiloxane, stearyl alcohol, polyoxypropylene glycerol, polyoxyethylene oxypropylene glycerol, and carboxy polydimethylsiloxane.
The second aspect of the invention provides a preparation method of a polyurethane hot melt adhesive for an automobile spare tire cover plate, which comprises the following steps:
(1) pretreatment of raw materials: adding a polymer with a hydroxyl end group, a crystalline alcohol modified copolyester, a polymer containing hydroxyl and alkoxy, random copolymerization polyolefin, an acrylic tackifier and a defoaming agent into a reaction kettle, heating, introducing nitrogen, stirring, cooling and vacuumizing to obtain a dehydrated raw material;
(2) preparing a hot melt adhesive: cooling the dehydrated raw materials in the step (1) to 60-90 ℃, adding an aromatic isocyanate compound at 80-85 ℃ under the condition of nitrogen to react for 20-60min, heating to 100-120 ℃, vacuumizing, adding amine and derivatives thereof, reacting with an organic silicon wetting agent, and discharging to obtain the polyurethane hot melt adhesive.
Wherein, the temperature in the step (1) is increased to 160 ℃ in the temperature range of 120-;
the temperature rise time in the step (2) is 20-60min, the amine and the derivatives thereof are added, the reaction time of the organic tin compound is 5-15min, and the reaction time of the organic silicon wetting agent is 1-10 min.
Compared with the prior art, the invention has the following beneficial effects:
1. when the polymer with the hydroxyl end group, the crystalline alcohol modified copolyester and the polymer containing the hydroxyl and the alkoxy are used simultaneously, the hydroxyl value of the polymer with the hydroxyl end group is 27-34mg KOH/g, the number average molecular weight of the crystalline alcohol modified copolyester is 3500, the viscosity of the polymer containing the hydroxyl and the alkoxy at 25 ℃ is 200-400cps, and particularly, when the weight ratio of the polymer with the hydroxyl end group, the crystalline alcohol modified copolyester and the polymer containing the hydroxyl and the alkoxy is 1; 2: 7, the strength and the weather resistance of the polyurethane hot melt adhesive can be obviously improved by interaction of the polyurethane hot melt adhesive and diphenylmethane diisocyanate in the system;
2. according to the polyurethane hot melt adhesive prepared by the invention, when dimorpholinodiethyl ether and dibutyltin dilaurate are added into a system and the weight percentage of dimorpholinodiethyl ether is controlled to be 0.5% and the weight percentage of dibutyltin dilaurate is controlled to be 0.004%, the polyurethane hot melt adhesive interacts with other components in the body, so that the weather resistance and the strength of the polyurethane hot melt adhesive are improved, meanwhile, the generation of byproducts in the system can be reduced, due to the special space structures of dimorpholinodiethyl ether and dibutyltin dilaurate, when the addition amount of the dimorpholinodiethyl ether and the dibutyltin dilaurate is strictly controlled, the curing time and the curing rate of the polyurethane hot melt adhesive are improved, the requirement of secondary activation within 2h of the hot melt adhesive is met, and the phenomenon that the felt surface in an automobile spare tire cover plate is easy to rebound and warp edges is effectively avoided;
3. according to the polyurethane hot melt adhesive prepared by the invention, when random copolymerization olefin is added into the system, particularly when the melt viscosity of the random copolymerization olefin at 190 ℃ is 8000mPa.s, the random copolymerization olefin can interact with other components in the system, so that the adhesion of the polyurethane hot melt adhesive on the surface of a glass fiber polypropylene composite board is improved, and the peel strength of the polyurethane hot melt adhesive is improved;
4. according to the polyurethane hot melt adhesive prepared by the invention, when the viscosity of a toluene solution with the mass concentration of 40% is 250-340mPa.s at 25 ℃ in the system, the viscosity of the system is improved, and the compatibility of dimorpholinodiethyl ether and dibutyltin dilaurate in the system is promoted on one hand; on the other hand, the leveling property and the diffusivity of the hot melt adhesive are improved, so that the viscosity of the system is in a certain range, the dual effects of enhancing the compatibility and the leveling property among all components are achieved, and the wettability and the initial viscosity of the polyurethane hot melt adhesive on the surface of the glass fiber polypropylene composite board are improved;
5. the polyurethane hot melt adhesive prepared by the invention has the advantages that the hydroxyl value is 27-34mg KOH/g, the polymer with the end group as the hydroxyl group, the crystalline alcohol modified copolyester with the number average molecular weight of 3500, the polymer with the viscosity of 200-400cps at 25 ℃ and diphenylmethane diisocyanate are introduced, auxiliaries such as dimorpholinodiethyl ether, dibutyltin dilaurate and the like are introduced into the polymer, the secondary activation can be realized within 2h by strictly controlling the proportion of the components, the adhesive force on the surface of the glass fiber polypropylene composite board is excellent, the problem that a felt surface in an automobile spare tire cover plate is easy to rebound and bridge edges is effectively solved, and the initial strength and the final strength are excellent.
Drawings
FIG. 1 is a graph showing the degree of controllability of the curing time of the polyurethane hot melt adhesives prepared in examples 1 to 3.
Wherein, A is example 2; b is example 3; c is example 1.
Detailed Description
Examples
Examples1
The polymer with the hydroxyl end group is purchased from Shanghai Kahn chemical Co., Ltd, the model is dynacoll 7380, and the hydroxyl value of the polymer with the hydroxyl end group is 27-34mg KOH/g;
the crystalline alcohol modified copolyester is purchased from Kay chemical company of Shanghai, with the model number of dynacoll 7360, and the number average molecular weight of the crystalline alcohol modified copolyester is 3500;
the polymer containing hydroxyl and alkoxy is purchased from Jiangsu clock and Shanshi Limited company, with the model number of N220, the viscosity of the polymer containing hydroxyl and alkoxy at 25 ℃ is 200-400cps, and the weight-average molecular weight is 2000;
the aromatic isocyanate compound is diphenylmethane diisocyanate, and the CAS number of the diphenylmethane diisocyanate is 101-68-8;
the amine and the derivative thereof are dimorpholinodiethylether, and the CAS number of the dimorpholinodiethylether is 6425-39-4;
the organic tin compound is dibutyltin dilaurate, and the CAS number of the dibutyltin dilaurate is 77-58-7;
the random copolymer polyolefin is purchased from Shanghai Kahn chemical Co., Ltd, and has the model of winning-creating VESSTOPLAST 508, and the melt viscosity of the random copolymer polyolefin at 190 ℃ is 8000 mPa.s;
the acrylic tackifier is purchased from Hebao plastic Co., Ltd, Dongguan and has the model of Mitsubishi BR113, and the viscosity of a 40 mass percent toluene solution of the acrylic tackifier at 25 ℃ is 250-340 mPa.s;
the antifoaming agent is octadecanol, and the CAS number of the octadecanol is 112-92-5;
the organic silicon wetting agent is purchased from Mianyanghan chemical new materials science and technology limited, and has the model number of E-520;
the preparation method of the polyurethane hot melt adhesive comprises the following steps:
(1) pretreatment of raw materials: adding a polymer with a hydroxyl end group, a crystalline alcohol modified copolyester, a polymer containing hydroxyl and alkoxy, random copolymerization polyolefin, an acrylic tackifier and a defoaming agent into a reaction kettle, heating, introducing nitrogen, stirring, cooling and vacuumizing to obtain a dehydrated raw material;
(2) preparing a hot melt adhesive: and (2) cooling the dehydrated raw materials in the step (1) to 80 ℃, adding an aromatic isocyanate compound to react for 40min at 85 ℃ under the condition of nitrogen, heating to 110 ℃, vacuumizing, adding amine and derivatives thereof, reacting with an organic tin compound, adding an organic silicon wetting agent to react, and discharging to obtain the polyurethane hot melt adhesive.
Wherein the temperature in the step (1) is raised to 150 ℃, the replacement time of introducing nitrogen is 30min, the stirring time is 1.5h, the temperature for reducing and vacuumizing is 125 ℃, and the vacuum degree for vacuumizing is less than or equal to 0.1 MPa;
the temperature rise time in the step (2) is 40min, the amine and the derivatives thereof are added, the reaction time of the organotin compound is 10min, and the reaction time of the organosilicon wetting agent is 5 min.
Examples2
The polymer with the hydroxyl end group is purchased from Shanghai Kahn chemical Co., Ltd, the model is dynacoll 7380, and the hydroxyl value of the polymer with the hydroxyl end group is 27-34mg KOH/g;
the crystalline alcohol modified copolyester is purchased from Kay chemical company of Shanghai, with the model number of dynacoll 7360, and the number average molecular weight of the crystalline alcohol modified copolyester is 3500;
the polymer containing hydroxyl and alkoxy is purchased from Jiangsu clock and Shanshi Limited company, with the model number of N220, the viscosity of the polymer containing hydroxyl and alkoxy at 25 ℃ is 200-400cps, and the weight-average molecular weight is 2000;
the aromatic isocyanate compound is diphenylmethane diisocyanate, and the CAS number of the diphenylmethane diisocyanate is 101-68-8;
the amine and the derivative thereof are dimorpholinodiethylether, and the CAS number of the dimorpholinodiethylether is 6425-39-4;
the organic tin compound is dibutyltin dilaurate, and the CAS number of the dibutyltin dilaurate is 77-58-7;
the random copolymer polyolefin is purchased from Shanghai Kahn chemical Co., Ltd, and has the model of winning-creating VESSTOPLAST 508, and the melt viscosity of the random copolymer polyolefin at 190 ℃ is 8000 mPa.s;
the acrylic tackifier is purchased from Hebao plastic Co., Ltd, Dongguan and has the model of Mitsubishi BR113, and the viscosity of a 40 mass percent toluene solution of the acrylic tackifier at 25 ℃ is 250-340 mPa.s;
the antifoaming agent is octadecanol, and the CAS number of the octadecanol is 112-92-5;
the organic silicon wetting agent is purchased from Mianyanghan chemical new materials science and technology limited, and has the model number of E-520;
the preparation method of the polyurethane hot melt adhesive is the same as that of example 1.
Examples3
The polymer with the hydroxyl end group is purchased from Shanghai Kahn chemical Co., Ltd, the model is dynacoll 7380, and the hydroxyl value of the polymer with the hydroxyl end group is 27-34mg KOH/g;
the crystalline alcohol modified copolyester is purchased from Kay chemical company of Shanghai, with the model number of dynacoll 7360, and the number average molecular weight of the crystalline alcohol modified copolyester is 3500;
the hydroxyl-and alkoxy-containing polymer is purchased from Jiangsu Ching Shanshi Kaishi Co., Ltd, is N220, has a viscosity of 200-400cps at 25 ℃ and a weight-average molecular weight of 2000;
the aromatic isocyanate compound is diphenylmethane diisocyanate, and the CAS number of the diphenylmethane diisocyanate is 101-68-8;
the amine and the derivative thereof are dimorpholinodiethylether, and the CAS number of the dimorpholinodiethylether is 6425-39-4;
the organic tin compound is dibutyltin dilaurate, and the CAS number of the dibutyltin dilaurate is 77-58-7;
the random copolymer polyolefin is purchased from Shanghai Kahn chemical Co., Ltd, and has the model of winning-creating VESSTOPLAST 508, and the melt viscosity of the random copolymer polyolefin at 190 ℃ is 8000 mPa.s;
the acrylic tackifier is purchased from Hebao plastic Co., Ltd, Dongguan and has the model of Mitsubishi BR113, and the viscosity of a 40 mass percent toluene solution of the acrylic tackifier at 25 ℃ is 250-340 mPa.s;
the antifoaming agent is octadecanol, and the CAS number of the octadecanol is 112-92-5;
the organic silicon wetting agent is purchased from Mianyanghan chemical new materials science and technology limited, and has the model number of E-520;
the preparation method of the polyurethane hot melt adhesive is the same as that of example 1.
Evaluation of Performance
(1) Peel Strength test
The polyurethane hot melt adhesive prepared in examples 1 to 3 was coated on a PVC sheet of 200mm × 25mm, and after pressing at 200 ℃ for 30s, the peel strength of the product was tested in accordance with GB/T2791-1995 "test method for peel strength of adhesive T", and the measured data are shown in Table 1;
(2) curing time controllability test
The polyurethane hot melt adhesive prepared in the examples 1 to 3 is coated on a PVC plate with the thickness of 200mm multiplied by 25mm, the PVC plate is placed in an environment with the temperature of 25 ℃ and the humidity of 50 percent, the content of isocyanate in the hot melt adhesive is detected, the lower the content of the isocyanate, the more complete the curing of the polyurethane hot melt adhesive is shown, and the test data are shown in figure 1;
TABLE 1
Claims (10)
1. The utility model provides a polyurethane hot melt adhesive for automobile spare tyre cover plate which characterized in that, the preparation raw materials include the following components: 5-10% of polymer with hydroxyl as end group, 10-20% of crystalline alcohol modified copolyester, 40-60% of polymer containing hydroxyl and alkoxy, 10-20% of aromatic isocyanate compound, 0.1-1% of amine and derivatives thereof, 0.002-0.006% of organic tin compound, 5-10% of random copolymerized polyolefin, 0.1-0.3% of defoaming agent, 0.4-0.6% of organic silicon wetting agent and the balance of acrylic tackifier.
2. The polyurethane hot melt adhesive according to claim 1, wherein the hydroxyl-terminated polymer has a hydroxyl number of 20 to 40mg KOH/g.
3. The polyurethane hot melt adhesive according to claim 1, wherein the polymer with hydroxyl end groups is a polymer obtained by polycondensation of at least one of monoacid, diacid, monoalcohol and diol.
4. The polyurethane hot melt adhesive as claimed in claim 1, wherein the number average molecular weight of the crystalline alcohol-modified copolyester is 2500-4500.
5. The polyurethane hot melt adhesive as claimed in claim 1, wherein the viscosity of the hydroxyl-and alkoxy-containing polymer at 25 ℃ is 100-600 cps.
6. The polyurethane hot melt adhesive according to claim 1 or 5, wherein the weight average molecular weight of the hydroxyl-and alkoxy-containing polymer is 500-3000.
7. The polyurethane hot melt adhesive according to any one of claims 1 to 6, wherein the weight ratio of the hydroxyl-terminated polymer, the crystalline alcohol-modified copolyester, and the hydroxyl-and alkoxy-containing polymer is 1; (1-3): (4-8).
8. The polyurethane hot melt adhesive according to claim 1, wherein the amine and the derivative thereof comprise at least one of dimorpholinodiethylether, N-methyldiethanolamine, and triethylenediamine.
9. The polyurethane hot melt adhesive according to claim 1, wherein the organic tin compound comprises at least one of dibutyl dilaurate and stannous octoate.
10. A method for preparing the polyurethane hot melt adhesive according to any one of claims 1 to 9, which is characterized by comprising the following steps:
(1) pretreatment of raw materials: adding a polymer with a hydroxyl end group, a crystalline alcohol modified copolyester, a polymer containing hydroxyl and alkoxy, random copolymerization polyolefin, an acrylic tackifier and a defoaming agent into a reaction kettle, heating, introducing nitrogen, stirring, cooling and vacuumizing to obtain a dehydrated raw material;
(2) preparing a hot melt adhesive: cooling the dehydrated raw materials in the step (1) to 60-90 ℃, adding an aromatic isocyanate compound at 80-85 ℃ under the condition of nitrogen to react for 20-60min, heating to 100-120 ℃, vacuumizing, adding amine and derivatives thereof, reacting with an organic silicon wetting agent, and discharging to obtain the polyurethane hot melt adhesive.
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| CN115991970A (en) * | 2022-12-12 | 2023-04-21 | 康达新材料(集团)股份有限公司 | Reactive polyurethane hot melt adhesive for automobile spare tire cover plate and preparation method thereof |
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