CN115584233A - Preparation process and application of high-toughness polyurethane adhesive - Google Patents
Preparation process and application of high-toughness polyurethane adhesive Download PDFInfo
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- CN115584233A CN115584233A CN202210160443.1A CN202210160443A CN115584233A CN 115584233 A CN115584233 A CN 115584233A CN 202210160443 A CN202210160443 A CN 202210160443A CN 115584233 A CN115584233 A CN 115584233A
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- Prior art keywords
- polyurethane adhesive
- polyester polyol
- toughness
- parts
- mixture
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- 239000004814 polyurethane Substances 0.000 title claims abstract description 45
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229920000728 polyester Polymers 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 76
- 239000000203 mixture Substances 0.000 claims description 35
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 15
- 150000003077 polyols Chemical class 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 6
- 239000013557 residual solvent Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 9
- 238000000034 method Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000013008 moisture curing Methods 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- -1 isocyanate siloxane Chemical class 0.000 description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 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 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 6
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- JLVWYWVLMFVCDI-UHFFFAOYSA-N diethyl benzene-1,3-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC(C(=O)OCC)=C1 JLVWYWVLMFVCDI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical group CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 3
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 3
- 238000003889 chemical engineering Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229940100573 methylpropanediol Drugs 0.000 description 3
- 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 2
- 239000002313 adhesive film Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 2
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- 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 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012205 single-component adhesive Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 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
-
- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to an adhesive (IPC classification number: C09J 167/00), in particular to a preparation process and application of a high-toughness polyurethane adhesive. Adding the polyalcohol and the auxiliary agent into a reaction kettle, heating, vacuumizing, cooling, adding the isocyanate and a part of solvent, introducing nitrogen, prepolymerizing, adding the catalyst, reacting, adding the silane modified polyester pre-product and the rest of solvent, cooling, and discharging to obtain the high-toughness polyurethane adhesive. The preparation process of the high-toughness polyurethane adhesive provided by the invention utilizes moisture curing reaction to form a film layer with sufficient toughness, and the film layer has excellent water washing resistance. The temperature and the charging sequence are strictly controlled, the smooth proceeding of the reaction is promoted, the intermediate working procedure of mixing ingredients is saved, the operation is more convenient, the crosslinking density of the high-toughness polyurethane adhesive is greatly increased, and the cohesive strength and the toughness of the colloid in the polyurethane adhesive are enhanced.
Description
Technical Field
The invention relates to an adhesive (IPC classification number: C09J 167/00), in particular to a preparation process and application of a high-toughness polyurethane adhesive.
Background
In recent years, with the development of the social and economic level, the application scene of the reflective cloth gradually expands towards the consumer market, and more clothes, bags, shoes and hats enterprises adopt the fabric with the reflective characteristic to increase the fashion attribute for products when designing the products. The novel products adapt to the requirements of consumer upgrading, the application field of the reflective cloth is greatly expanded, wide market space is brought, and the conventional fancy reflective cloth mainly adopts two-component solvent type glue and two-component solvent type glue, so that the following problems are mainly caused: (1) the amount of sizing is limited; (2) The pattern integrity is poor, and the appearance problems of trailing, wire drawing, glue shortage and the like exist; (3) The adhesive is applied to fabrics, and has more limitation, for example, hydrophobic cloth is difficult to bond; and (4) the overall performance of the glue is poor in water washing resistance.
Chinese patent with patent publication number CN201911117230.5 discloses an anti-yellowing two-liquid type polyurethane adhesive for a reflective material and a preparation method thereof, IPDI and H are adopted in the Chinese patent 12 When the isocyanate of MDI is used in cooperation with other raw materials, the prepared polyurethane adhesive has good water resistance and weather resistance and is improved when used for a reflective material.
Therefore, the high-toughness polyurethane adhesive is synthesized through specific process steps, an adhesive film layer with sufficient toughness and good elasticity is formed by utilizing moisture curing reaction, the high-toughness polyurethane adhesive has excellent washing resistance, intermediate procedures of mixing ingredients are saved, the operation is convenient, and the pattern effect is clear on the transfer of a large-size concave roller, and no wire drawing or tailing occurs.
Disclosure of Invention
The invention provides a preparation process of a high-toughness polyurethane adhesive, which comprises the following steps:
(1) Adding polyester polyol A, polyester polyol B1, polyester polyol C and cross-linking polyether polyol into a reaction kettle, heating, dehydrating and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent accounting for 10-30% of the weight of the mixture A, introducing nitrogen, carrying out prepolymerization reaction, adding a catalyst, and continuing to react to obtain a mixture B;
(3) And adding the silane modified polyester prepolymer and the residual solvent into the mixture B, cooling and discharging to obtain the adhesive.
As a preferable scheme, the heating temperature in the step (1) is 110-120 ℃;
as a preferable scheme, the heating temperature in the step (1) is 100 ℃;
as a preferable scheme, the temperature for reducing the temperature in the step (2) is less than 80 ℃;
as a preferable scheme, the temperature for reducing the temperature in the step (2) is 40-60 ℃;
as a preferable scheme, the time of the prepolymerization in the step (2) is 20-40min;
as a preferable mode, the time of the prepolymerization in the step (2) is 30min;
as a preferred scheme, the time for continuing the reaction in the step (2) is more than 2h;
as a preferable scheme, the time for continuing the reaction in the step (2) is 3 to 4 hours;
as a preferred scheme, the mass percent of the-NCO in the mixture B in the step (2) is 1-3wt%;
as a preferable scheme, the temperature of the temperature reduction in the step (3) is less than 55 ℃;
as a preferable scheme, the temperature for reducing the temperature in the step (3) is 30-40 ℃;
as a preferable scheme, the viscosity of the adhesive obtained in the step (3) is 800-3000mpa.s,25 ℃; the solid content of the adhesive is more than 60 percent.
As a preferable scheme, the raw materials for preparing the high-toughness polyurethane adhesive comprise, by weight, 30-50 parts of polyester polyol A, 5-20 parts of polyester polyol B, 10-30 parts of polyester polyol C, 0-5 parts of crosslinking type polyether polyol, 5-30 parts of isocyanate, 5-50 parts of solvent, 0.01-0.2 part of catalyst and 0-15 parts of silane modified polyester prepolymer;
as a preferred scheme, the number average molecular weight of the polyester polyol A is 2000-2500g/mol;
in a preferred embodiment, the polyester polyol a is a crystalline polyester polyol obtained by polycondensation of one or more of isophthalic acid, phthalic anhydride, terephthalic acid, dimethyl isophthalate, dimethyl terephthalate, diethyl isophthalate, and diethyl terephthalate, and one or more of adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid, with one or more of methylpropanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, trimethylpentanediol, ethylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, and diethylene glycol.
As a preferable scheme, the polyester polyol B1 has a number average molecular weight of 2000 +/-100 g/mol;
in a preferred embodiment, the polyester polyol B1 is a polycondensate of one or more of suberic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid and tetradecanedioic acid with one or more of methylpropanediol, neopentyl glycol, 3-methyl-1,5-pentanediol and trimethylpentanediol.
As a preferred embodiment, the number average molecular weight of the polyester polyol C is 4000. + -. 100g/mol;
in a preferred embodiment, the polyester polyol C is a crystalline polyester polyol obtained by polycondensation of one or more of isophthalic acid, terephthalic acid, dimethyl isophthalate, diethyl isophthalate, dimethyl terephthalate, diethyl terephthalate, one or more of adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid, with one or more of methylpropanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, trimethylpentanediol, ethylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, and diethylene glycol.
Preferably, the weight ratio of the polyester polyol A, the polyester polyol B1 and the polyester polyol C is (3.5-4.5): 1: (1.5-2).
As a preferable mode, the hydroxyl value of the crosslinking polyether polyol is 950 +/-10 mgKOH/g;
as a preferred embodiment, the isocyanate is a mixture of hydrogenated diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI);
as a preferable scheme, the weight ratio of the HMDI to the IPDI is (1-2): 1.
as a preferred embodiment, the solvent is anhydrous ethyl acetate.
In a preferred embodiment, the catalyst is bismuth isooctanoate.
As a preferred embodiment, the silane-modified polyester prepolymer is a reaction product of a polyester polyol B2 and an isocyanate siloxane.
As a preferable scheme, the isocyanate siloxane is one or more of 3-isocyanate propyl methyl diethoxy silane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane and 3-isocyanate propyl triethoxy silane.
As a preferred embodiment, the isocyanate siloxane is 3-isocyanatopropylmethyldiethoxysilane.
As a preferred embodiment, the preparation method of the silane modified polyester prepolymer comprises the following steps: (1) Adding polyester polyol B2 into a reactor, heating, vacuumizing, cooling, and introducing nitrogen; (2) Adding isocyanate siloxane, and reacting to obtain the silane modified polyester prepolymer.
As a preferable scheme, the polyester polyol B2, the isocyanate siloxane weight ratio is 10: (2-4).
As a preferable scheme, the polyester polyol B2, the isocyanate siloxane weight ratio is 10:3.
the polyester polyol B1 and the polyester polyol B2 in the present invention are the same.
The preparation process of the high-toughness polyurethane adhesive provided by the invention synthesizes a high-solid-content single-component adhesive, utilizes a moisture curing reaction to form an adhesive film layer with sufficient toughness and good elasticity, and has excellent washing resistance. The prepolymer synthesis method is adopted, the danger of spraying materials caused by the release of a large amount of heat in a one-pot method is avoided, meanwhile, the temperature and the feeding sequence are strictly controlled, the smooth proceeding of the reaction is promoted, the intermediate working procedure of mixing ingredients is saved, the operation is more convenient, the crosslinking density of the high-toughness polyurethane adhesive is greatly increased, and the cohesive strength and the toughness of the colloid in the polyurethane adhesive are enhanced. The preparation process of the high-toughness polyurethane adhesive has clear pattern effect, and does not draw wires or trail when being transferred on a large-size concave roller.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation process of the high-toughness polyurethane adhesive provided by the invention adopts a prepolymer synthesis method, avoids the danger of material spraying caused by a large amount of heat released by a one-pot method, and is beneficial to smooth reaction;
2. according to the preparation process of the high-toughness polyurethane adhesive, when the prepolymerization reaction time is strictly controlled to be 20-40min and the continuous reaction time is 3-4 h, the viscosity of a reaction system is prevented from being further increased, so that the stability of the prepared polyurethane adhesive is influenced, and the integrity of the fancy reflective patterns is ensured.
3. According to the preparation process of the high-toughness polyurethane adhesive, when the mass percent of-NCO in the mixture B is strictly controlled to be 1-3wt%, the uniform reaction is facilitated, the viscosity of a reaction system is ensured, the generation of side reactions is reduced, the stability of a product is improved, and the gluing amount is increased.
4. According to the preparation process of the high-toughness polyurethane adhesive, the initial bonding strength and the final bonding strength of the polyurethane adhesive are improved through the synergistic effect of the polyester polyol A with the number average molecular weight of 2000-2500g/mol, the polyester polyol B1 with the number average molecular weight of 2000 +/-100 g/mol and the polyester polyol C with the number average molecular weight of 4000 +/-100 g/mol, and meanwhile, the water resistance and the toughness of the polyurethane adhesive are improved.
5. According to the preparation process of the high-toughness polyurethane adhesive, when the hydroxyl value of the cross-linked polyether polyol is limited to 950 +/-10 mgKOH/g, the cross-linking degree of the polymer is improved, the cohesive strength is improved, a good network structure is formed, and the polyurethane adhesive has excellent toughness and elasticity.
Drawings
Fig. 1 is a microscope image of a finished fancy reflective fabric prepared in comparative example 1.
Fig. 2 is a microscope image of the finished fancy reflective fabric prepared in comparative example 2.
Detailed Description
Examples
Examples1
Embodiment 1 provides a preparation process of a high-toughness polyurethane adhesive, comprising the following steps:
(1) Adding polyester polyol A, polyester polyol B1, polyester polyol C and cross-linking polyether polyol into a reaction kettle, heating, dehydrating and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent which accounts for 20% of the weight of the mixture A, introducing nitrogen, carrying out prepolymerization reaction, adding a catalyst, and continuing to react to obtain a mixture B;
(3) And adding the silane modified polyester prepolymer and the residual solvent into the mixture B, cooling and discharging to obtain the adhesive.
The heating temperature in the step (1) is 100 ℃;
the temperature for cooling in the step (2) is 50 ℃;
the time of the prepolymerization reaction in the step (2) is 30min;
the reaction is continued for 3.5 hours in the step (2);
the mass percent of-NCO in the mixture B in the step (2) is 2wt%;
the temperature of the temperature reduction in the step (3) is 30 ℃;
the preparation raw materials of the high-toughness polyurethane adhesive in the embodiment comprise the following components in parts by weight: 40 parts of polyester polyol A, 10 parts of polyester polyol B, 18 parts of polyester polyol C, 3 parts of cross-linking polyether polyol, 15 parts of isocyanate, 42 parts of solvent, 0.1 part of catalyst and 10 parts of silane modified polyester prepolymer.
The polyester polyol A in this example was purchased from PDP-70 of Su Telin (Nanjing) New Material science and technology Ltd
The polyester polyol C in this example was purchased from PA-56N of Nanjing Handhel-Manual-chemical engineering science and technology Limited liability company
The cross-linked polyether polyol in this example was purchased from sepiline 3095, france.
The isocyanate in this example is a mixture of hydrogenated diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI);
in this embodiment, the weight ratio of HMDI to IPDI is 2:1.
the solvent in this example was anhydrous ethyl acetate.
The catalyst in this example was bismuth isooctanoate.
The silane-modified polyester prepolymer in this example is the reaction product of polyester polyol B2 and an isocyanate siloxane.
In the polyester polyol B2 in this example, the weight ratio of isocyanate siloxane was 10:3.
the isocyanate siloxane in this example was 3-isocyanatopropylmethyldiethoxysilane.
In this embodiment, the preparation method of the silane modified polyester prepolymer includes the following steps: (1) Adding polyester polyol B2 into a reactor, heating, vacuumizing, cooling, and introducing nitrogen; (2) Adding isocyanate siloxane, and reacting to obtain the silane modified polyester prepolymer.
In this example, the polyester polyols B1 and B2 are the same.
The high molecular weight polyester polyol in this example is a condensation polymer of diethyl isophthalate, adipic acid, and neopentyl glycol.
The number average molecular weight of the high molecular weight polyester polyol in this embodiment is 4000g/mol.
The high molecular weight polyester polyol in this example is Shandong national chemical Co., ltd.
Examples2
Embodiment 2 provides a preparation process of a high-toughness polyurethane adhesive, comprising the following steps:
(1) Adding polyester polyol A, polyester polyol B1, polyester polyol C and cross-linking polyether polyol into a reaction kettle, heating, dehydrating and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent which accounts for 20% of the weight of the mixture A, introducing nitrogen, carrying out prepolymerization reaction, adding a catalyst, and continuing to react to obtain a mixture B;
(3) And adding the silane modified polyester prepolymer and the residual solvent into the mixture B, cooling and discharging to obtain the adhesive.
The heating temperature in the step (1) is 120 ℃;
the temperature for cooling in the step (2) is 60 ℃;
the time of the prepolymerization reaction in the step (2) is 40min;
the reaction is continued for 4 hours in the step (2);
the mass percent of-NCO in the mixture B in the step (2) is 2wt%;
the temperature of the temperature reduction in the step (3) is 30 ℃;
the preparation raw materials of the high-toughness polyurethane adhesive in the embodiment comprise the following components in parts by weight: 40 parts of polyester polyol A, 10 parts of polyester polyol B, 18 parts of polyester polyol C, 3 parts of cross-linking polyether polyol, 15 parts of isocyanate, 42 parts of solvent, 0.1 part of catalyst and 10 parts of silane modified polyester prepolymer.
The polyester polyol A in this example was purchased from PDP-70 of Su Telin (Nanjing) New Material science and technology Ltd
The polyester polyol C in this example was purchased from PA-56N of Nanjing Handhel-Manual-chemical engineering science and technology Limited liability company
The cross-linked polyether polyol in this example was purchased from sepiline 3095, france.
The isocyanate in this example is a mixture of hydrogenated diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI);
in this embodiment, the weight ratio of HMDI to IPDI is 2:1.
the solvent in this example was anhydrous ethyl acetate.
The catalyst in this example was bismuth isooctanoate.
The silane-modified polyester prepolymer in this example is the reaction product of polyester polyol B2 and an isocyanate siloxane.
The silane-modified polyester prepolymer in this example was 3-isocyanatopropylmethyldiethoxysilane.
In this example, the polyester polyols B1 and B2 are the same.
The high molecular weight polyester polyol in this example is a condensation polymer of diethyl isophthalate, adipic acid, and neopentyl glycol.
The number average molecular weight of the high molecular weight polyester polyol in this embodiment is 4000g/mol.
The high-molecular-weight polyester polyol in the present example is Shandong national chemical Co., ltd.
In this embodiment, the preparation method of the silane modified polyester prepolymer includes the following steps: (1) Adding polyester polyol B2 into a reactor, heating, vacuumizing, cooling, and introducing nitrogen; (2) Adding isocyanate siloxane, and reacting to obtain the silane modified polyester prepolymer.
Examples3
Embodiment 3 provides a preparation process of a high-toughness polyurethane adhesive, comprising the following steps:
(1) Adding polyester polyol A, polyester polyol B1, polyester polyol C and cross-linking polyether polyol into a reaction kettle, heating, dehydrating and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent which accounts for 20% of the weight of the mixture A, introducing nitrogen, carrying out prepolymerization reaction, adding a catalyst, and continuing to react to obtain a mixture B;
(3) And adding the silane modified polyester prepolymer and the residual solvent into the mixture B, cooling and discharging to obtain the adhesive.
The heating temperature in the step (1) is 110 ℃;
the temperature for cooling in the step (2) is 40 ℃;
the time of the prepolymerization reaction in the step (2) is 30min;
the reaction is continued for 3 hours in the step (2);
the mass percent of-NCO in the mixture B in the step (2) is 1wt%;
the temperature of the temperature reduction in the step (3) is 30 ℃;
the preparation raw materials of the high-toughness polyurethane adhesive in the embodiment comprise the following components in parts by weight: 40 parts of polyester polyol A, 10 parts of polyester polyol B, 18 parts of polyester polyol C, 3 parts of cross-linking polyether polyol, 15 parts of isocyanate, 42 parts of solvent, 0.1 part of catalyst and 10 parts of silane modified polyester prepolymer.
The polyester polyol A in this example was purchased from PDP-70 of Su Telin (Nanjing) New Material science and technology Ltd
The polyester polyol C in this example was purchased from PA-56N of Nanjing Handhel-Manual-chemical engineering science and technology Limited liability company
The cross-linked polyether polyol in this example was purchased from sepiline 3095, france.
The isocyanate in this example is a mixture of hydrogenated diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI);
in this embodiment, the weight ratio of HMDI to IPDI is 2:1.
the solvent in this example was anhydrous ethyl acetate.
The catalyst in this example was bismuth isooctanoate.
The silane-modified polyester prepolymer in this example is the reaction product of polyester polyol B2 and an isocyanate siloxane.
The silane-modified polyester prepolymer in this example was 3-isocyanatopropylmethyldiethoxysilane.
In this example, the polyester polyols B1 and B2 are the same.
The high molecular weight polyester polyol in this example is a condensation polymer of diethyl isophthalate, adipic acid, and neopentyl glycol.
The number average molecular weight of the high molecular weight polyester polyol in this embodiment is 4000g/mol.
The high molecular weight polyester polyol in this example is Shandong national chemical Co., ltd.
In this embodiment, the preparation method of the silane modified polyester prepolymer includes the following steps: (1) Adding polyester polyol B2 into a reactor, heating, vacuumizing, cooling, and introducing nitrogen; (2) Adding isocyanate siloxane, and reacting to obtain the silane modified polyester prepolymer.
Comparative example1
Comparative example 1 the specific embodiment is the same as example 1 except that the prepolymerization time in step (2) is 1 hour.
Comparative example2
Comparative example 2 the specific embodiment is the same as example 3 except that the heating temperature in step (1) is 150 ℃.
And (3) performance testing:
(1) Solid content: firstly weighing a clean watch glass with the mass of W, and then weighing W 1 The sample was dried in a petri dish at 120 ℃ for 3h, cooled to room temperature and weighed as W 2 The emulsion has a solid content of = (W2-W)/W1 × l00%.
(2) Coating effect: directly pouring the prepared adhesive into a trough containing ethyl acetate, performing fancy coating on a reflective bead-planted film, drying the ethyl acetate through a drying tunnel, then compounding with chemical fiber cloth, controlling the compounding temperature at 50 ℃, rolling after compounding, and stripping after the glue absorbs water vapor and is cured at normal temperature to form a film to obtain a fancy reflective cloth finished product, wherein the coating thickness of the adhesive is 30 mu m, and the coating effect is visually observed.
Table 1 shows the solid content and coating effect performance test table of the high-toughness polyurethane adhesives prepared in examples 1-3 and comparative examples 1-2.
TABLE 1
Claims (10)
1. A preparation process of a high-toughness polyurethane adhesive comprises the following steps:
(1) Adding polyester polyol A, polyester polyol B1, polyester polyol C and cross-linking polyether polyol into a reaction kettle, heating, dehydrating and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent accounting for 20% of the weight of the mixture A, introducing nitrogen, carrying out prepolymerization reaction, adding a catalyst, and continuing the reaction to obtain a mixture B;
(3) And adding the silane modified polyester prepolymer and the residual solvent into the mixture B, cooling and discharging to obtain the adhesive.
2. The process for preparing a high-toughness polyurethane adhesive according to claim 1, wherein the heating temperature in step (1) is 110-120 ℃.
3. The process for preparing the high-toughness polyurethane adhesive according to claim 1, wherein the temperature for reducing the temperature in the step (2) is less than 80 ℃.
4. The process for preparing the high-toughness polyurethane adhesive according to claim 1, wherein the time of the prepolymerization reaction in the step (2) is 20-40min.
5. The process for preparing the high-toughness polyurethane adhesive according to claim 1, wherein the continuous reaction time in the step (2) is more than 2 hours.
6. The process for preparing a high-toughness polyurethane adhesive according to claim 1, wherein the mass percentage of-NCO in the mixture B in the step (2) is 1 to 3wt%.
7. The process for preparing the high-toughness polyurethane adhesive according to claim 1, wherein the reaction time in the step (1) is 15-30min.
8. The process for preparing a high-toughness polyurethane adhesive according to claim 1, wherein the raw materials used in the process for preparing a high-toughness polyurethane adhesive comprise, in parts by weight: 30-50 parts of polyester polyol A, 5-20 parts of polyester polyol B, 10-30 parts of polyester polyol C, 0-5 parts of cross-linked polyether polyol, 5-30 parts of isocyanate, 5-50 parts of solvent, 0.01-0.2 part of catalyst and 0-15 parts of silane modified polyester prepolymer.
9. The process for preparing a high-toughness polyurethane adhesive according to claim 8, wherein the number average molecular weight of the polyester polyol A is 2000 to 2500g/mol.
10. Use of a high tenacity polyurethane adhesive according to any of claims 8 to 9 in fancy reflective cloth.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295815A (en) * | 2015-11-11 | 2016-02-03 | 上海康达化工新材料股份有限公司 | Reactive polyurethane hot melt adhesive for reflective fabric and preparation method thereof |
| CN107001556A (en) * | 2014-11-24 | 2017-08-01 | Sika技术股份公司 | Fast curing compositions containing silane group |
| CN107383353A (en) * | 2017-08-31 | 2017-11-24 | 浙江道明光电科技有限公司 | A kind of preparation method of silane-modified polyester prepolyer |
| CN111253899A (en) * | 2020-03-23 | 2020-06-09 | 泰安聚仁新材料有限公司 | Industrial water washing resistant bright silver reflective fabric adhesive and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001556A (en) * | 2014-11-24 | 2017-08-01 | Sika技术股份公司 | Fast curing compositions containing silane group |
| CN105295815A (en) * | 2015-11-11 | 2016-02-03 | 上海康达化工新材料股份有限公司 | Reactive polyurethane hot melt adhesive for reflective fabric and preparation method thereof |
| CN107383353A (en) * | 2017-08-31 | 2017-11-24 | 浙江道明光电科技有限公司 | A kind of preparation method of silane-modified polyester prepolyer |
| CN111253899A (en) * | 2020-03-23 | 2020-06-09 | 泰安聚仁新材料有限公司 | Industrial water washing resistant bright silver reflective fabric adhesive and preparation method thereof |
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