CN113583613A - High-heat-resistance polyurethane adhesive and preparation method thereof - Google Patents
High-heat-resistance polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN113583613A CN113583613A CN202110985908.2A CN202110985908A CN113583613A CN 113583613 A CN113583613 A CN 113583613A CN 202110985908 A CN202110985908 A CN 202110985908A CN 113583613 A CN113583613 A CN 113583613A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 81
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 27
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- -1 polybutylene Polymers 0.000 claims description 13
- 229920001748 polybutylene Polymers 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- LLOXZCFOAUCDAE-UHFFFAOYSA-N 2-diphenylphosphorylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(P(=O)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 LLOXZCFOAUCDAE-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 8
- 230000004927 fusion Effects 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 abstract description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000126 substance Substances 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
- C09J175/06—Polyurethanes from polyesters
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of polyurethane adhesives, in particular to a high-heat-resistance polyurethane adhesive and a preparation method thereof. The feed comprises the following raw materials: polyurethane prepolymer, copolymer resin, filler, heat-resistant agent, solvent, catalyst and dispersant; the added heat-resistant agent can generate a flame-retardant carbonized layer when the adhesive is heated due to the addition of the phosphorus additive, the strength of the adhesive can be improved by adding the filler, meanwhile, the flame retardance of the adhesive is greatly increased due to the addition of various oxides, and the metal oxides in the filler and the heat-resistant agent rich in a large amount of phosphoric acid elements are reacted to produce an acidified phosphorus oxide product, and the product can be used for acidifying the copolymer resin to produce phosphoric acid modified copolymer resin, so that the modified resin has better fusion force with the prepolymer, and the adhesive force and the flame retardance of the adhesive are further improved.
Description
Technical Field
The invention relates to the technical field of polyurethane adhesives, in particular to a high-heat-resistance polyurethane adhesive and a preparation method thereof.
Background
The polyurethane adhesive is an important component in polyurethane resin which is rapidly developed at present, has excellent performance, is widely applied in many aspects, is one of eight important varieties of synthetic adhesives, has excellent shear strength and impact resistance, is suitable for various structural bonding fields, has excellent flexibility, has strong bonding force, and also has excellent buffering and damping functions, the low-temperature and ultralow-temperature performance of the polyurethane adhesive exceeds that of all other types of adhesives, and the thermoplastic polyurethane adhesive is a synthetic polyurethane adhesive made of thermoplastic polyurethane, is softened and bonded when being heated, and is hardened after being cooled to have certain strength.
The existing polyurethane adhesive has poor heat resistance, is very easy to melt at high temperature after being cured, and simultaneously, because the addition of chemicals in the adhesive is excessive, the melting point of the adhesive is reduced, and the flame retardance is reduced, so that the defect of the prior art is overcome by the high-heat-resistance polyurethane adhesive.
Disclosure of Invention
The present invention is directed to a polyurethane adhesive with high heat resistance and a preparation method thereof, so as to solve the problems mentioned in the background art.
In order to achieve the above object, in one aspect, the present invention provides a polyurethane adhesive with high heat resistance, which comprises the following raw materials: 130 parts of polyurethane prepolymer, 20-30 parts of copolymer resin, 12-17 parts of filler, 1-5 parts of heat-resistant agent, 30-50 parts of solvent, 0.1-3 parts of catalyst and 0.1-3 parts of dispersant;
the heat-resistant agent is one or more of 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide, diphenyl phosphorus oxide, ditolyl bis diphenyl phosphine oxide, pentaerythritol phosphate and triphenyl phosphate, and is used for improving the heat resistance of the adhesive.
As a further improvement of the technical scheme, the polyurethane prepolymer is synthesized by the reaction of polybutylene glycol oxalate and diisocyanate, wherein the molecular weight of the polybutylene glycol oxalate is 2000-6000 g/Pmol.
As a further improvement of the technical scheme, the copolymer resin is selected from one or more of epoxy resin, acrylic resin, rosin resin, phenolic resin, terpene resin and petroleum resin, and can further increase the viscosity of the adhesive.
As a further improvement of the technical scheme, the filler is selected from a plurality of mixtures of alumina powder, mica powder, quartz powder, titanium dioxide powder, magnesium powder, silicon dioxide powder and ferric oxide powder, the strength of the adhesive can be improved by adding the filler, and meanwhile, the flame retardance of the adhesive is greatly increased due to the addition of various oxides.
As a further improvement of the technical scheme, the solvent is at least one of toluene, acetic acid, chlorobenzene and cyclohexanone.
As a further improvement of the technical scheme, the catalyst is dibutyltin dilaurate.
As a further improvement of the technical scheme, the dispersing agent is selected from one of ethylene-vinyl acetate and ethylene-acrylic acid.
In another aspect, the present invention provides a method for preparing a polyurethane adhesive having high heat resistance as described in any one of the above, comprising the steps of;
s1, adding the polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
s2, adding diisocyanate, stirring, adding a catalyst, and performing prepolymerization to obtain a polyurethane prepolymer;
s3, adding the polyurethane prepolymer, the copolymer resin, the filler, the heat-resistant agent and the dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder to perform extrusion molding to obtain granules;
and S4, adding the master batch into a solvent, and dissolving to obtain the polyurethane adhesive.
Preferably, in S2, the temperature is 90-110 ℃, and the rotation speed is 200-220 r/min.
Preferably, in S3, the heating temperature is 100-120 ℃, and the rotation speed is 500-600 r/min.
In the invention, the metal oxide in the filler reacts with the heat-resistant agent rich in a large amount of phosphoric acid elements to produce an acidified phosphorus oxide product, the product can be used for acidifying the copolymer resin to produce phosphoric acid modified copolymer resin, the modified resin has better fusion force with the prepolymer, and the adhesive force and the flame retardance of the adhesive are further improved.
Compared with the prior art, the invention has the beneficial effects that:
1. in the polyurethane adhesive with high heat resistance and the preparation method thereof, the added heat-resistant agent can generate a flame-retardant carbonized layer when the adhesive is heated due to the increase of the phosphorus additive.
2. According to the high-heat-resistance polyurethane adhesive and the preparation method thereof, the strength of the adhesive can be improved by adding the filler, meanwhile, the flame retardance of the adhesive is greatly increased due to the addition of various oxides, and the metal oxides in the filler react with the heat-resistant agent rich in a large amount of phosphoric acid elements to produce an acidified phosphorus oxide product, the product can be used for acidifying the copolymer resin to produce phosphoric acid modified copolymer resin, the modified resin and the prepolymer have good fusion force, and the adhesive force and the flame retardance of the adhesive are further improved.
Drawings
FIG. 1 is an overall flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:
1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;
3. adding 130 parts of polyurethane prepolymer, 20 parts of copolymer resin, 12 parts of filler, 1 part of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;
4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.
Embodiment 2 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:
1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;
3. adding 125 parts of polyurethane prepolymer, 22.5 parts of copolymer resin, 13 parts of filler, 2 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;
4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.
Example 3 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:
1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;
3. adding 120 parts of polyurethane prepolymer, 25 parts of copolymer resin, 15 parts of filler, 3 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 120 ℃ and the rotating speed is 600 r/min;
4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.
Example 4 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:
1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;
3. adding 15 parts of polyurethane prepolymer, 27.5 parts of copolymer resin, 16 parts of filler, 4 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;
4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.
Example 5 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:
1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;
3. adding 110 parts of polyurethane prepolymer, 30 parts of copolymer resin, 17 parts of filler, 5 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;
4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.
In the adhesive, the heat-resistant agent is one or more selected from 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide, diphenyl phosphorus oxide, ditolyl bis diphenyl phosphine oxide, pentaerythritol phosphate and triphenyl phosphate, and is used for improving the heat resistance of the adhesive;
the molecular weight of the polybutylene glycol oxalate glycol is 2000-6000 g/Pmol;
the copolymer resin is selected from one or more of epoxy resin, acrylic resin, rosin resin, phenolic resin, terpene resin and petroleum resin, and can further increase the viscosity of the adhesive; the filler is selected from a plurality of mixtures of alumina powder, mica powder, quartz powder, titanium dioxide powder, magnesium powder, silicon dioxide powder and ferric oxide powder, the strength of the adhesive can be improved by adding the filler, meanwhile, the flame retardance of the adhesive is greatly increased due to the addition of various oxides, and metal oxides in the filler react with a heat-resistant agent rich in a large amount of phosphoric acid elements to produce an acidified phosphorus oxide product which can be used for acidifying the copolymer resin to produce phosphoric acid modified copolymer resin, the modified resin has better fusion force with a prepolymer, and the adhesive force and the flame retardance of the adhesive are further improved;
at least one of solvents toluene, acetic acid, chlorobenzene and cyclohexanone;
the catalyst is dibutyltin dilaurate;
the dispersant is selected from one of ethylene-vinyl acetate and ethylene-acrylic acid.
The indexes of the polyurethane adhesive with high heat resistance in examples 1-5 of the present invention are specifically shown in table 1:
TABLE 1
As shown in Table 1, the high heat-resistant polyurethane adhesives prepared in examples 1-5 of the present invention all have good tensile strength and peel strength, and the heat distortion temperature is above 350 ℃, and the oxygen index also meets the flame retardant standard, so that the high heat-resistant polyurethane adhesives prepared in the present invention have good heat resistance and strength.
Comparative example 1 a polyurethane adhesive having high heat resistance and a method for preparing the same, comprising:
1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;
3. adding 120 parts of polyurethane prepolymer, 25 parts of copolymer resin, 15 parts of filler and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;
4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.
Comparative example 2 a polyurethane adhesive having high heat resistance and a method for preparing the same, comprising:
1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;
3. adding 120 parts of polyurethane prepolymer, 15 parts of filler, 3 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;
4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.
Comparative example 3 a polyurethane adhesive having high heat resistance and a method for preparing the same, comprising:
1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;
3. adding 120 parts of polyurethane prepolymer, 25 parts of copolymer resin, 3 parts of heat-resistant agent and 2 parts of dispersing agent into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;
4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.
The polyurethane adhesive with high heat resistance prepared by the invention has better heat resistance and strength, has a great relationship with the added heat-resistant agent, the added copolymer resin and the added filler, and in order to verify the related technical scheme, the applicant performs the following tests:
comparative examples 1 to 3: by adopting the method of example 3, the relevant indexes of the prepared adhesive are detected under the condition that the heat-resistant agent, the copolymer resin and the filler are removed, and the concrete indexes are shown in table 2:
TABLE 2
As shown in table 2, when the heat-resistant agent is removed, the thermal deformation temperature and the oxygen index of the adhesive decrease greatly, when the copolymer resin is removed, the peeling strength of the adhesive decreases greatly, and when the filler is removed, the tensile strength and the elongation at break of the adhesive decrease significantly, so that it can be shown that adding the heat-resistant agent, the copolymer resin and the filler in the adhesive production process is an important factor for changing the heat resistance and the strength of the adhesive.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The polyurethane adhesive with high heat resistance is characterized by comprising the following raw materials: 130 parts of polyurethane prepolymer, 20-30 parts of copolymer resin, 12-17 parts of filler, 1-5 parts of heat-resistant agent, 30-50 parts of solvent, 0.1-3 parts of catalyst and 0.1-3 parts of dispersant;
the heat-resistant agent is selected from one or more of 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide, diphenyl phosphorus oxide, ditolyl bis diphenyl phosphine oxide, pentaerythritol phosphate and triphenyl phosphate.
2. The high heat resistant polyurethane adhesive according to claim 1, wherein: the polyurethane prepolymer is synthesized by the reaction of butanediol adipate glycol and diisocyanate, wherein the molecular weight of the butanediol adipate glycol is 2000-6000 g/Pmol.
3. The high heat resistant polyurethane adhesive according to claim 1, wherein: the copolymer resin is selected from one or more of epoxy resin, acrylic resin, rosin resin, phenolic resin, terpene resin and petroleum resin.
4. The high heat resistant polyurethane adhesive according to claim 1, wherein: the filler is selected from a plurality of mixtures of alumina powder, mica powder, quartz powder, titanium dioxide powder, magnesium powder, silicon dioxide powder and ferric oxide powder.
5. The high heat resistant polyurethane adhesive according to claim 1, wherein: at least one of the solvents toluene, acetic acid, chlorobenzene and cyclohexanone.
6. The high heat resistant polyurethane adhesive according to claim 1, wherein: the catalyst is dibutyltin dilaurate.
7. The high heat resistant polyurethane adhesive according to claim 1, wherein: the dispersing agent is selected from one of ethylene-vinyl acetate and ethylene-acrylic acid.
8. A method for preparing the high heat-resistant polyurethane adhesive according to any one of claims 1 to 7, comprising the steps of;
s1, adding the polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;
s2, adding diisocyanate, stirring, adding a catalyst, and performing prepolymerization to obtain a polyurethane prepolymer;
s3, adding the polyurethane prepolymer, the copolymer resin, the filler, the heat-resistant agent and the dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder to perform extrusion molding to obtain granules;
and S4, adding the master batch into a solvent, and dissolving to obtain the polyurethane adhesive.
9. The method of preparing a polyurethane adhesive having high heat resistance as set forth in claim 8, wherein: in the S2, the temperature is 90-110 ℃, and the rotation speed is 200-220 r/min.
10. The method of preparing a polyurethane adhesive having high heat resistance as set forth in claim 8, wherein: in the S3, the heating temperature is 100-120 ℃, and the rotation speed is 500-600 r/min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504751A (en) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | Flame-retardant polyurethane sealant and preparation method thereof |
| CN107936902A (en) * | 2017-12-06 | 2018-04-20 | 苏州铂邦胶业有限公司 | Flame-retardant polyurethane sealant |
-
2021
- 2021-08-26 CN CN202110985908.2A patent/CN113583613A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504751A (en) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | Flame-retardant polyurethane sealant and preparation method thereof |
| CN107936902A (en) * | 2017-12-06 | 2018-04-20 | 苏州铂邦胶业有限公司 | Flame-retardant polyurethane sealant |
Non-Patent Citations (3)
| Title |
|---|
| 曹惟诚 等: "《胶接技术手册》", 31 August 1988, 上海科学技术出版社 * |
| 沈一丁 等: "《轻化工助剂》", 31 July 2004, 中国轻工业出版社 * |
| 韦军: "《高分子合成工艺学》", 28 February 2011, 华东理工大学出版社 * |
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