CN105542700A - Single-component polyurethane adhesive and preparation method thereof - Google Patents
Single-component polyurethane adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN105542700A CN105542700A CN201511006198.5A CN201511006198A CN105542700A CN 105542700 A CN105542700 A CN 105542700A CN 201511006198 A CN201511006198 A CN 201511006198A CN 105542700 A CN105542700 A CN 105542700A
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- Prior art keywords
- agent
- polyurethane adhesive
- raw material
- component polyurethane
- solvent
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Links
- 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 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 72
- 239000002994 raw material Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 24
- 239000004902 Softening Agent Substances 0.000 claims description 21
- 150000005846 sugar alcohols Polymers 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 14
- 229920005906 polyester polyol Polymers 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 235000005979 Citrus limon Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- YUEDZVRMWQBEPT-UHFFFAOYSA-N CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O Chemical compound CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O YUEDZVRMWQBEPT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 229960005082 etohexadiol Drugs 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229960005150 glycerol Drugs 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002274 desiccant Substances 0.000 abstract 3
- 239000004014 plasticizer Substances 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 239000003292 glue Substances 0.000 description 11
- 241001070947 Fagus Species 0.000 description 9
- 235000010099 Fagus sylvatica Nutrition 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010008 shearing Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 244000131522 Citrus pyriformis Species 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 206010020675 Hypermetropia Diseases 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
- C08G18/307—Atmospheric humidity
-
- 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
- C09J175/08—Polyurethanes from polyethers
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 a single-component polyurethane adhesive and a preparation method thereof. The single-component polyurethane adhesive comprises an adhesive and a quick-drying agent. The adhesive is prepared from 0-3% of dibasic alcohol, 15-50% of polymer polylol, 30-70% of isocyanate, 0-0.3% of catalyst, 0-25% of solvent and 0-15% of plasticizer, totaling 100%. The quick-drying agent is prepared from 1-50% of catalyst, 0-80% of solvent, 0-80% of plasticizer, 0.1-15% of silane coupling agent, 0-10% of dibasic alcohol, 0-10% of polylol and 10-20% of polymer polylol, totaling 100%. The quick-drying agent accounts for 0-10% of the adhesive. The single-component polyurethane adhesive has the advantages of high storage stability and adjustable curing speed, and can adapt to different technological conditions and operating environment temperatures.
Description
Technical field
The present invention relates to adhesive area, particularly relate to a kind of one-component polyurethane adhesive and preparation method thereof.
Background technology
Polyurethane adhesive is generally divided into one-component polyurethane adhesive and dual-component polyurethane adhesive.
Dual-component polyurethane adhesive is generally made up of A, B two components, and during use, two components according to certain proportioning, need stir, and A, B component are not used alone; The glue be simultaneously stirred must be finished in the short period of time, and especially at high temperature season, after glue mixing, viscosity increases very fast, and cause the later stage to use difficulty, a large amount of glue is scrapped and maybe can not be formed good bonding, produces a large amount of unacceptable product.But due to A, B two component separately deposit, therefore storage stability is higher, generally can reach even more than 1 year half a year.
One-component polyurethane adhesive is generally NCO group end-blocking, can directly use in production process, easy and simple to handle, and glue is long for working life, and in operation on the same day, glue viscosity can not acutely increase, very little to technogenic influence.But comparatively dual-component polyurethane adhesive is slow usually for one-component polyurethane adhesive curing speed, especially in low temperature environment, even wants could solidify for more than 24 hours.In order to improve curing speed, as directly added catalyzer at one-component polyurethane adhesive, the reaction of moisture in its storage process easily and in air, cause the phenomenon such as skinning, caking, the shelf lives is shorter, and the severe patient shelf lives is even less than 1 month.
Summary of the invention
Based on this, be necessary for the problems referred to above, one-component polyurethane adhesive providing a kind of curing speed adjustable and preparation method thereof.
For realizing above-mentioned technical purpose, concrete technical scheme is as follows:
A kind of one-component polyurethane adhesive, comprise tackiness agent and quick dry agent, wherein, by weight percentage, the raw material of described tackiness agent comprises: dibasic alcohol 0 ~ 3%, polymerized polyalcohol 15 ~ 50%, isocyanic ester 30 ~ 70%, catalyzer 0 ~ 0.3%, solvent 0 ~ 25%, softening agent 0 ~ 15%, and the summation of above-mentioned raw materials is 100%;
The raw material of described quick dry agent comprises: catalyzer 1 ~ 50%, solvent 0 ~ 80%, softening agent 0 ~ 80%, silane coupling agent 0.1 ~ 15%, dibasic alcohol 0 ~ 10%, polyvalent alcohol 0 ~ 10%, polymerized polyalcohol 10 ~ 20%, and the summation of above-mentioned raw materials is 100%;
The addition of described quick dry agent is 0 ~ 10% of described tackiness agent;
Described catalyzer is one or more the mixture in organo-bismuth, organotin, trolamine, triethylene diamine, triethylene tetramine, four ethene triamines or five ethene tetramines.
Wherein in some embodiments, by weight percentage, the raw material of described tackiness agent comprises: dibasic alcohol 0 ~ 1%, polymerized polyalcohol 20 ~ 45%, isocyanic ester 30 ~ 65%, catalyzer 0 ~ 0.2%, solvent 0 ~ 25%, softening agent 0 ~ 15%, and the summation of above-mentioned raw materials is 100%;
The raw material of described quick dry agent comprises: catalyzer 10 ~ 50%, solvent 0 ~ 80%, softening agent 0 ~ 80%, silane coupling agent 0.5 ~ 10%, dibasic alcohol 0 ~ 5%, polyvalent alcohol 0 ~ 10%, polymerized polyalcohol 12 ~ 18%, and the summation of above-mentioned raw materials is 100%.
Wherein in some embodiments, by weight percentage, the raw material of described tackiness agent comprises: polymerized polyalcohol 29 ~ 31%, isocyanic ester 59 ~ 61%, solvent 9 ~ 11%, and the summation of above-mentioned raw materials is 100%; The raw material of described quick dry agent comprises: catalyzer 20 ~ 22%, polymerized polyalcohol 14 ~ 16%, silane coupling agent 7 ~ 9%, softening agent 9 ~ 11%, solvent 45 ~ 47%, and the summation of above-mentioned raw materials is 100%; The addition of described quick dry agent is 4.9 ~ 5.1% of described tackiness agent.
Wherein in some embodiments, described dibasic alcohol is one or more the mixture in butyleneglycol, pentanediol, hexylene glycol, ethohexadiol.
Wherein in some embodiments, described polymerized polyalcohol is polyether glycol and/or polyester polyol.
Wherein in some embodiments, described polyvalent alcohol is one or more the mixture in glycerine, tetramethylolmethane, Xylitol, sorbyl alcohol.
Wherein in some embodiments, described isocyanic ester is one or more the mixture in tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dimethyl triphenyl methane tetraisocyanate.
Wherein in some embodiments, described solvent is one or more the mixture in methyl acetate, ethyl acetate, butylacetate, acetone, butanone; Described softening agent is one or more the mixture in tributyl citrate, trioctyl lemon acid, tributyl acetylcitrate, ATOC.
The present invention also provides a kind of preparation method of above-mentioned one-component polyurethane adhesive, comprises the steps:
(1) tackiness agent is prepared: take each raw material according to said ratio, described isocyanic ester is poured in stirring tank, after being heated to 70 ~ 90 DEG C, adding described polymerized polyalcohol and stir, often add a kind of described polymerized polyalcohol reaction 0.5 ~ 2h, reduce temperature of charge after reaction to 49 ~ 51 DEG C; When raw material comprises described solvent, softening agent and catalyzer, then in the end add described solvent, softening agent and catalyzer and stir, reaction 0.5 ~ 1h, obtains tackiness agent;
(2) prepare quick dry agent: take each raw material according to said ratio, described polymerized polyalcohol is poured in stirring tank, when described raw material packet is containing described dibasic alcohol, polyvalent alcohol, then pour described dibasic alcohol, polyvalent alcohol into stirring tank in the lump; After being heated to 60 ~ 80 DEG C, add described silane coupling agent to stir, reaction 0.5 ~ 1h, then temperature of charge is reduced to 40 ~ 50 DEG C, add described catalyzer to stir, reaction 0.5 ~ 1h, when described raw material comprises described solvent and softening agent, then in the end add described solvent and softening agent stirs, obtain quick dry agent.
Wherein in some embodiments, when described raw material comprises described dibasic alcohol, then before reducing temperature of charge to the step of 49 ~ 51 DEG C, add described dibasic alcohol and stir, reaction 0.5 ~ 1h.
The present inventor team is main raw material by large quantity research preferred polymeric polyvalent alcohol and isocyanic ester, under specific processing condition, makes the tackiness agent in the polyurethane adhesive of the present invention of NCO end-blocking.Owing to optimizing kind and the proportioning of isocyanic ester and polymerized polyalcohol, this tackiness agent has good storage stability.And the quick dry agent in polyurethane adhesive of the present invention adopts special preferred silane coupling agent, define the catalyzer of parcel, the catalyzer of high level in this package structure, can be held.When quick dry agent and binding agent mixing, the structure of outer layer covers is only when steam and NCO group exist jointly, and just meeting Unclosing structure, discharges a large amount of catalyzer.Therefore when the present invention is coated on substrate surface, glue-line is thinner, and a large amount of catalyzer is released, and improves cured later speed as quick as thought.And the polyurethane adhesive be stored in container, due to isolated air, therefore there is good stability in storage and longer operating time.
The present invention compares the advantage of prior art and beneficial effect is:
(1) raw material such as preferred polymeric polyvalent alcohol of the present invention, isocyanic ester, under specific processing condition, prepared the tackiness agent in the present invention, it has good storage stability;
(2) the present invention the is preferred raw material such as silane coupling agent, catalyzer, under the processing condition of feature, prepare the quick dry agent in the present invention with special package structure, unit volume can wrap up more substantial catalyzer, thus be honored as a queen by solution completely at catalyzer, can present faster stronger catalytic effect, breach the catalysis limit in the past, curing speed is multiplied;
(3) the one-component polyurethane adhesive not only storage-stable for preparing of the present invention, client can environmentally need with technique etc. and regulate the consumption of quick dry agent simultaneously, regulate curing speed, different processing condition and different operating environment temperature can be adapted to, greatly improve the handiness of operation.
Accompanying drawing explanation
Fig. 1 is shearing resistance performance test schematic diagram.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
The all raw materials of the present invention are commercially available common raw material, wherein:
Polyester polyol I-stickpolyol160 rises novel material science and technology purchased from Guangzhou is farsighted;
Polyester polyol I-stickpolyolY rises novel material science and technology purchased from Guangzhou is farsighted;
Polyether glycol PPG-400, PPG-2000, BDO are purchased from DOW Chemical;
Silane coupling agent SilquestA-187, SilquestA-Link597 are purchased from Momentive company;
Isocyanic ester: Suprasec2020, Suprasec3056 are purchased from Huntsman;
Dibutyl tin laurate is purchased from Basf;
Ethyl acetate, acetone are purchased from Guangzhou solvent factory;
Trioctyl lemon acid is purchased from the sub-chemical industry of Shenzhen China;
Triethylene diamine is purchased from air chemical industry;
Catalyst I-stickcatalyst001 rises novel material science and technology purchased from Guangzhou is farsighted.
Embodiment 1
A kind of one-component polyurethane adhesive, is made up of tackiness agent and quick dry agent:
Tackiness agent raw material composition and weight percentage be: the polyether glycol PPG-2000 of 46%, the isocyanic ester Suprasec2020 of 51%, 3% dibasic alcohol BDO.
Quick dry agent composition and weight percentage be: the catalyst dibutyltin dilaurylate of 20%, the polyester polyol I-stickpolyolY of 15%, 5% silane coupling agent SilquestA-187, the silane coupling agent SilquestA-Link597 of 10%, the solvent ethyl acetate of 50%.
The present embodiment adds the quick dry agent component of glue paste weight 2%.
The preparation method of above-mentioned one-component polyurethane adhesive, comprises the steps:
(1) tackiness agent is prepared: percentage composition accurately takes each raw material by weight, isocyanic ester Suprasec2020 is poured in stirring tank, after 70 ~ 90 DEG C are heated to stirring tank, add polyether glycol PPG2000 and stir, sealed reaction 2h, control temperature of charge between 70 ~ 90 DEG C, add BDO to stir, sealed reaction 1h, reduce temperature of charge to 50 DEG C, obtain tackiness agent;
(2) quick dry agent is prepared: percentage composition accurately takes each raw material by weight, I-stickPolyolY is poured in stirring tank, after being heated to 80 DEG C, add SilquestA-187 to stir, reaction 0.5h, then temperature of charge is reduced to 60 DEG C, add SilquestA-Link597 to stir, reaction 0.5h, then reduces temperature of charge to 50 DEG C, adds dibutyl tin laurate and stir, reaction 0.5h, finally control temperature of charge and be no more than 50 DEG C, add ethyl acetate and stir, obtain quick dry agent.
Embodiment 2
A kind of one-component polyurethane adhesive, is made up of tackiness agent and quick dry agent:
Tackiness agent raw material composition and weight percentage be: the polyether glycol PPG-400 of 15%, the polyester polyol I-stickpolyol160 of 7%, 55% isocyanic ester Suprasec3056, the dibasic alcohol BDO of 1%, solvent ethyl acetate, the solvent acetone of 8%, the catalyst I-stickcatalyst001 of 0.3% of 13.7%.
Quick dry agent composition and weight percentage be: the catalyst dibutyltin dilaurylate of 18%, the catalyzer triethylene diamine of 2%, 15% polyester polyol I-stickpolyolY, the silane coupling agent SilquestA-187 of 3%, silane coupling agent SilquestA-Link597, the solvent ethyl acetate of 50%, the solvent acetone of 7% of 5%.
The present embodiment adds the quick dry agent component of Different Weight with differing temps, as shown in table 2 below.
The preparation method of above-mentioned one-component polyurethane adhesive, comprises the steps:
(1) tackiness agent is prepared: percentage composition accurately takes each raw material by weight, isocyanic ester Suprasec3056 is poured in stirring tank, after 70 ~ 90 DEG C are heated to stirring tank, add polyether glycol PPG400 to stir, sealed reaction 1h, add polyester polyol I-stickpolyol160 again to stir, sealed reaction 1h, control temperature of charge between 70 ~ 90 DEG C, add 1, 4-butyleneglycol stirs, sealed reaction 1h, reduce temperature of charge to 50 DEG C, add ethyl acetate, acetone and I-stickcatalyst001 stir, sealed reaction 0.5h, obtain tackiness agent,
(2) quick dry agent is prepared: percentage composition accurately takes each raw material by weight, I-stickPolyolY is poured in stirring tank, after being heated to 80 DEG C, add SilquestA-187 to stir, reaction 0.5h, then temperature of charge is reduced to 60 DEG C, add SilquestA-Link597 to stir, reaction 0.5h, then reduces temperature of charge to 50 DEG C, adds dibutyl tin laurate and triethylene diamine stirs, reaction 0.5h, finally control temperature of charge and be no more than 50 DEG C, add ethyl acetate and acetone stirs, obtain quick dry agent.
Embodiment 3
A kind of one-component polyurethane adhesive, is made up of tackiness agent and quick dry agent:
Tackiness agent raw material composition and weight percentage be: the polyester polyol I-stickpolyol160 of 30%, the isocyanic ester Suprasec3056 of 60%, 10% solvent ethyl acetate.
Quick dry agent composition and weight percentage are: the catalyst dibutyltin dilaurylate of 20%, the catalyzer triethylene diamine of 1%, the polyester polyol I-stickpolyolY of 15%, silane coupling agent SilquestA-187, the silane coupling agent SilquestA-Link597 of 5%, the softening agent trioctyl lemon acid of 10% of 3%, the solvent ethyl acetate of 46%.
The present embodiment adds the quick dry agent component of glue paste weight 5%.
The preparation method of above-mentioned one-component polyurethane adhesive, comprises the steps:
(1) tackiness agent is prepared: percentage composition accurately takes each raw material by weight, isocyanic ester Suprasec3056 is poured in stirring tank, after 70 ~ 90 DEG C are heated to stirring tank, add polyester polyol I-stickpolyol160 to stir, sealed reaction 2h, reduces temperature of charge to 50 DEG C, adds ethyl acetate and stir, sealed reaction 0.5h, obtains tackiness agent;
(2) quick dry agent is prepared: percentage composition accurately takes each raw material by weight, I-stickPolyolY is poured in stirring tank, after being heated to 80 DEG C, add SilquestA-187 to stir, reaction 0.5h, then temperature of charge is reduced to 60 DEG C, add SilquestA-Link597 to stir, reaction 0.5h, then reduces temperature of charge to 50 DEG C, adds dibutyl tin laurate and triethylene diamine stirs, reaction 0.5h, finally control temperature of charge and be no more than 50 DEG C, add trioctyl lemon acid and ethyl acetate stirs, obtain quick dry agent.
Application experiment
1, working life testing method: with reference to GB/T2794-1995
Respectively by the tackiness agent in polyurethane adhesive prepared in embodiment 1 ~ 3 and quick dry agent under the in situ temperature shown in table 1 ~ 3, in proportion, mixed by dispersion machine (stirring 3 minutes under 800rpm rotating speed).Then start stopwatch, the viscosity number of glue after one minute test mixing, when glue viscosity reach or just more than 100,000mpa.s time, be defined as terminal, the time is now working life.
2, shearing resistance performance test (see Fig. 1): with reference to GB7124-1986.
Instrument: automatic gas press, drawing machine, precision is the measurer of 1mm.
Test piece: water ratio 10 ± 2%, density 700 ± 100Kg/m
3beech (25 × 30 × 10).
The preparation of sample: glue is coated on splicing face, splicing area is 25mm × 25mm, Amount of spread 100g/m
2, by automatic sample press two pieces of test pieces are coincided and glued joint into sample, apply 0.1-0.2N/mm
2pressure.
Test procedure:
(1) length and the width of part is gluedd joint with gage measuring sample;
(2) ready sample is placed in fixture, executed power should be made parallel to each other, start drawing machine, write down load maximum when pressurized is sheared.
Method of calculation:
(1) calculating of shearing resistance: δ=P/ (L × B)
In formula: δ---shearing resistance, Mpa or N/mm
2
Ultimate load during P---sample fracture, N
L---sample glueds joint the length of part, mm
B---sample glueds joint the width of part, mm
(2) sample representing same performance is generally no less than five
When carrying out shearing resistance performance test, the polyurethane adhesive of the embodiment of the present invention, before being administered to base material, be guaranteed fully to mix;
By applying constant voltage on automatic press, the base material for compression shear test is standard beech, and its length × wide × height corresponds to 30 × 25 × 10mm
3;
In situ temperature error is no more than 1 DEG C;
Bonding overlapping area is 25 × 25mm
2.
The application of the embodiment of the present invention 1 ~ 3 gained polyurethane adhesive in base material beech/beech:
Respectively the tackiness agent in polyurethane adhesive prepared in embodiment 1 ~ 3 and quick dry agent are applied to the bonding of beech/beech in the ratio shown in table 1 ~ 3.Mixed under the in situ temperature shown in table 1 ~ 3 respectively by each formula, and be coated on base material beech/beech, pressurization for some time, as shown in following table 1 ~ 3.Test shearing resistance described above, result is shown in following table 1 ~ 3.
The each performance comparison of embodiment 1 under table 1. differing temps
The each performance comparison of embodiment 2 under table 2. differing temps
The each performance comparison of embodiment 3 under table 3. differing temps
Under normal circumstances, for beech/beech, when shearing resistance is more than 2Mpa, bonding base material can meet and is relaxed and carries out the requirement of light processing.As can be seen from table 1 ~ 3, one-component polyurethane adhesive in embodiment all has very long working life (>8h) in the scope of 0-30 DEG C so wide, even if with the addition of quick dry agent, under same day operational condition, working life is not also almost significantly affected.One-component polyurethane adhesive of the present invention is (temperature >=25 DEG C) under summer environment, and by regulating the consumption of quick dry agent, what can reach client in 1 ~ 2 hour unloads pressure request, and this improves the production efficiency of client exponentially.Even if in low temperature environment, between 0-10 DEG C, what also can ensure to reach in 2-3 hour client unloads pressure request, ensures the production capacity of client at low temperature season.
Simultaneous test
One-component polyurethane adhesive of the present invention and commercially available traditional one-component polyurethane adhesive and traditional dual-component polyurethane adhesive are carried out simultaneous test, and test-results is as shown in table 4:
Table 4 product of the present invention and commercially available prod performance comparison
As can be seen from the above table, the relatively commercially available one-component polyurethane adhesive 1 or 2 of polyurethane adhesive of the present invention all has the longer quality guaranteed period, is conducive to reducing waste product, facilitates client to arrange tank farm stock flexibly simultaneously.The relatively commercially available dual-component polyurethane adhesive 1 or 2 of polyurethane adhesive of the present invention all has longer working life and curing speed faster, facilitates the operation of client, reduces glue waste, and finally improves Total Product quality.According to AOF calculation, use polyurethane adhesive of the present invention, the production capacity of client is 1.6-6 times that uses one-component polyurethane adhesive; 2-4 times that uses dual-component polyurethane adhesive, the economic benefit highly significant that it directly brings, and the economic benefit indirectly brought thus cannot be estimated especially.
Each technical characteristic of the above embodiment can combine arbitrarily, for making description succinct, the all possible combination of each technical characteristic in above-described embodiment is not all described, but, as long as the combination of these technical characteristics does not exist contradiction, be all considered to be the scope that this specification sheets is recorded.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an one-component polyurethane adhesive, it is characterized in that, comprise tackiness agent and quick dry agent, wherein, by weight percentage, the raw material of described tackiness agent comprises: dibasic alcohol 0 ~ 3%, polymerized polyalcohol 15 ~ 50%, isocyanic ester 30 ~ 70%, catalyzer 0 ~ 0.3%, solvent 0 ~ 25%, softening agent 0 ~ 15%, and the summation of above-mentioned raw materials is 100%;
The raw material of described quick dry agent comprises: catalyzer 1 ~ 50%, solvent 0 ~ 80%, softening agent 0 ~ 80%, silane coupling agent 0.1 ~ 15%, dibasic alcohol 0 ~ 10%, polyvalent alcohol 0 ~ 10%, polymerized polyalcohol 10 ~ 20%, and the summation of above-mentioned raw materials is 100%;
The addition of described quick dry agent is 0 ~ 10% of described tackiness agent;
Described catalyzer is one or more the mixture in organo-bismuth, organotin, trolamine, triethylene diamine, triethylene tetramine, four ethene triamines or five ethene tetramines.
2. one-component polyurethane adhesive according to claim 1, it is characterized in that, by weight percentage, the raw material of described tackiness agent comprises: dibasic alcohol 0 ~ 1%, polymerized polyalcohol 20 ~ 45%, isocyanic ester 30 ~ 65%, catalyzer 0 ~ 0.2%, solvent 0 ~ 25%, softening agent 0 ~ 15%, and the summation of above-mentioned raw materials is 100%;
The raw material of described quick dry agent comprises: catalyzer 10 ~ 50%, solvent 0 ~ 80%, softening agent 0 ~ 80%, silane coupling agent 0.5 ~ 10%, dibasic alcohol 0 ~ 5%, polyvalent alcohol 0 ~ 10%, polymerized polyalcohol 12 ~ 18%, and the summation of above-mentioned raw materials is 100%.
3. one-component polyurethane adhesive according to claim 2, is characterized in that, by weight percentage, the raw material of described tackiness agent comprises: polymerized polyalcohol 29 ~ 31%, isocyanic ester 59 ~ 61%, solvent 9 ~ 11%, and the summation of above-mentioned raw materials is 100%; The raw material of described quick dry agent comprises: catalyzer 20 ~ 22%, polymerized polyalcohol 14 ~ 16%, silane coupling agent 7 ~ 9%, softening agent 9 ~ 11%, solvent 45 ~ 47%, and the summation of above-mentioned raw materials is 100%; The addition of described quick dry agent is 4.9 ~ 5.1% of described tackiness agent.
4. the one-component polyurethane adhesive according to any one of claims 1 to 3, is characterized in that, described dibasic alcohol is one or more the mixture in butyleneglycol, pentanediol, hexylene glycol, ethohexadiol.
5. the one-component polyurethane adhesive according to any one of claims 1 to 3, is characterized in that, described polymerized polyalcohol is polyether glycol and/or polyester polyol.
6. the one-component polyurethane adhesive according to any one of claims 1 to 3, is characterized in that, described polyvalent alcohol is one or more the mixture in glycerine, tetramethylolmethane, Xylitol, sorbyl alcohol.
7. the one-component polyurethane adhesive according to any one of claims 1 to 3, it is characterized in that, described isocyanic ester is one or more the mixture in tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dimethyl triphenyl methane tetraisocyanate.
8. the one-component polyurethane adhesive according to any one of claims 1 to 3, is characterized in that, described solvent is one or more the mixture in methyl acetate, ethyl acetate, butylacetate, acetone, butanone; Described softening agent is one or more the mixture in tributyl citrate, trioctyl lemon acid, tributyl acetylcitrate, ATOC.
9. a preparation method for the one-component polyurethane adhesive described in any one of claim 1 ~ 8, is characterized in that, comprises the steps:
(1) tackiness agent is prepared: take each raw material according to proportioning described in any one of claims 1 to 3, described isocyanic ester is poured in stirring tank, after being heated to 70 ~ 90 DEG C, add described polymerized polyalcohol to stir, often add a kind of described polymerized polyalcohol reaction 0.5 ~ 2h, reduce temperature of charge after reaction to 49 ~ 51 DEG C; When raw material comprises described solvent, softening agent and catalyzer, then in the end add described solvent, softening agent and catalyzer and stir, reaction 0.5 ~ 1h, obtains tackiness agent;
(2) quick dry agent is prepared: take each raw material according to proportioning described in any one of claims 1 to 3, described polymerized polyalcohol is poured in stirring tank, when described raw material packet is containing described dibasic alcohol, polyvalent alcohol, then pour described dibasic alcohol, polyvalent alcohol into stirring tank in the lump; After being heated to 60 ~ 80 DEG C, add described silane coupling agent to stir, reaction 0.5 ~ 1h, then temperature of charge is reduced to 40 ~ 50 DEG C, add described catalyzer to stir, reaction 0.5 ~ 1h, when described raw material comprises described solvent and softening agent, then in the end add described solvent and softening agent stirs, obtain quick dry agent.
10. the preparation method of one-component polyurethane adhesive according to claim 9, it is characterized in that, when described raw material comprises described dibasic alcohol, then before reducing temperature of charge to the step of 49 ~ 51 DEG C, add described dibasic alcohol and stir, reaction 0.5 ~ 1h.
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| CN105801912B (en) * | 2016-05-17 | 2018-08-31 | 石家庄东翔化工有限公司 | Coordinate the external application drying aid and the preparation method and application thereof of cranny filler of polyurethane foam |
| EP3404073A1 (en) * | 2017-05-19 | 2018-11-21 | Evonik Degussa GmbH | Hydrophilic isocyanurates containing aloxysilane |
| CN109467735A (en) * | 2018-11-12 | 2019-03-15 | 重庆迅昌汽车零部件有限公司 | A kind of preparation method of monocomponent polyurethane sealing strip |
| CN110540624A (en) * | 2019-07-18 | 2019-12-06 | 中山市马里奥机械科技有限公司 | Full-automatic production line and production process of polyurethane adhesive |
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| CN105801912B (en) * | 2016-05-17 | 2018-08-31 | 石家庄东翔化工有限公司 | Coordinate the external application drying aid and the preparation method and application thereof of cranny filler of polyurethane foam |
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| CN109467735A (en) * | 2018-11-12 | 2019-03-15 | 重庆迅昌汽车零部件有限公司 | A kind of preparation method of monocomponent polyurethane sealing strip |
| CN110540624A (en) * | 2019-07-18 | 2019-12-06 | 中山市马里奥机械科技有限公司 | Full-automatic production line and production process of polyurethane adhesive |
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| CN105542700B (en) | 2018-09-07 |
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