CN101418203A - Single component moisture curing high strength polyurethane adhesive - Google Patents
Single component moisture curing high strength polyurethane adhesive Download PDFInfo
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- CN101418203A CN101418203A CNA2007100537187A CN200710053718A CN101418203A CN 101418203 A CN101418203 A CN 101418203A CN A2007100537187 A CNA2007100537187 A CN A2007100537187A CN 200710053718 A CN200710053718 A CN 200710053718A CN 101418203 A CN101418203 A CN 101418203A
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Abstract
The invention is called as a single-composition moisturecuring high-strength polyurethane adhesive and belongs to the technical field of the single-composition moisturecuring polyurethane adhesive. The adhesive is mainly to solve the problems that the prior single-composition moisturecuring polyurethane adhesive has unhigh tensile strength and tearing strength as well as poor storage stability at room temperature. The single-composition moisturecuring high-strength polyurethane adhesive has the following main characteristics: the adhesive comprises 8 to 20 weight portions of polyurethane prepolymer (II) prepared from polyether glycol, chain extender, isocyanate, atalyst and thinner, 20 to 50 weight portions of polyurethane prepolymer (I) prepared from polyether glycol, chain extender, isocyanate and thinner and 30 to 60 weight portions of plasticizer, filler and catalyst, wherein the use amount of the chain extender is 45 to 50 percent of that the polyurethane prepolymer (II); and the use amount of the chain extender is 50 to 60 percent of that of the polyurethane prepolymer (I). The single-composition moisturecuring high-strength polyurethane adhesive has the characteristics that the tensile strength reaches 13.3 MPa; the tearing strength reaches 54.7 KN/m; the storage period at the room temperature reaches 2 years; and the adhesive is mainly used for assembly and maintenance of high-grade automobiles.
Description
Technical field
The invention belongs to the monocomponent moisture cure urethanes adhesive technical field, the single component moisture curing high strength polyurethane adhesive that relates to medium-to-high grade automobile loading and maintenance usefulness, its bonding strength height, good springiness, ageing-resistant, anti-various organic solvents directly are adhered to automobile wind shield glass on the vehicle window frame and finish simultaneously sealing.
Background technology
General Motors Overseas Corporation at first developed " the direct assembling method of car glass " in 1961, and this assembly technology is with adhesive/sealant and other annexes the car windshield directly to be adhered to also to finish sealing on the vehicle window frame simultaneously.20th century the mid-1970s, the american car production begins to adopt monocomponent moisture cure type polyurethane adhesive/sealant to come bonding glass for vehicle window, its bonding strength height, good springiness, ageing-resistant, anti-various organic solvents, and use also more convenient.The bonding seal gum of urethane can combine glass for vehicle window and vehicle body as a whole securely, improves car body ground rigidity and anti-twist ability, and sealing property is obviously improved.Security, reliability increase considerably, and can alleviate the vehicle body deadweight simultaneously.Automobile is progressively popularized in China with the production application of polyurethane adhesive at present, and the existing homemade glue in the maintenance market with glue market and domestic car of low and middle-grade cars occupies, and its tensile strength is generally all about 5MPa.And requiring tensile strength greater than 8MPa to high-grade automobile loading land used polyurethane adhesive, elongation is greater than 400%.The monocomponent moisture cure urethanes adhesive of prior art, the H-131 of the AM-1501 in home-made such as chemical plant, Shandong, Shenzhen letter three pines, its tensile strength is the highest all has only 8MPa, the tensile strength of the BETASEAL HV3 of external product technology such as DOW chemistry Wuhan ESSEXS company only is 9 ± 1MPa, the tensile strength of Henkel TEROSTAT 8690 HM only is 8.5MPa, the tensile strength of the single-component moisture curing polyurethane glue of other foreign brand names all find to surpass 10MPa's, finds no the storage period of product to surpass 9 months.
In the monocomponent moisture cure urethanes adhesive of prior art in the polyurethane prepolymer molecular weight of polyether glycol generally 1000～5000, generalized case is that two functionality and three-functionality-degree polyethers, high molecular and low molecular polyether collocation are used, make polyurethane prepolymer, molecular weight is generally in 10000.Wherein polyurethane prepolymer content is 40%～55%, and other polyurethane adhesives are 45%～60% with the content of other raw materials such as softening agent, filler and catalyzer.
The monocomponent moisture cure urethanes adhesive of prior art has the following disadvantages:
(1) the monocomponent moisture cure urethanes adhesive tensile strength of prior art does not generally all surpass 10Mpa.
(2) the monocomponent moisture cure urethanes adhesive tear strength of prior art does not generally all surpass 35KN/m.
(3) the monocomponent moisture cure urethanes adhesive room temperature storage stability of prior art generally all is no more than one-year age.
Summary of the invention
The invention provides a kind of single component moisture curing high strength polyurethane adhesive, can use at medium-to-high grade automobile loading, its bonding strength height, good springiness, ageing-resistant, anti-various organic solvents directly are adhered to automobile wind shield glass on the vehicle window frame and finish simultaneously sealing.
Technical solution of the present invention is: a kind of single component moisture curing high strength polyurethane adhesive, it is characterized in that comprising:
(a) 8～20 weight parts are H-[O-(R based on described single component moisture curing high strength polyurethane adhesive by polyether glycol, structural formula
2)
5-CO-] m-O-R
1-O-[CO-(R
2)
5-O] n-NHCO-R
3The polyurethane prepolymer (II) made of chainextender, isocyanic ester, catalyzer, thinner, wherein the consumption of chainextender accounts for 45%～50% He of polyurethane prepolymer (II) consumption
(b) 20～50 weight parts are H-[O-(R based on described single component moisture curing high strength polyurethane adhesive by polyether glycol, structural formula
2)
5-CO-] m-O-R
1-O-[CO-(R
2)
5-O] n-NHCO-R
3The polyurethane prepolymer (I) made of chainextender, isocyanic ester, thinner, wherein the consumption of chainextender accounts for 50%～60% He of polyurethane prepolymer (I) consumption
(c) 30～60 weight parts are based on polyurethane adhesive softening agent, filler and the catalyzer of described single component moisture curing high strength polyurethane adhesive.
The consumption of polyurethane prepolymer (II) is 9～18 weight parts in the optimisation technique solution of the present invention, and the consumption of polyurethane prepolymer (I) is 25～48 weight parts, and polyurethane adhesive is 37～55 weight parts with softening agent, filler and catalyst consumption.
The consumption of polyurethane prepolymer (II) is 10～17 weight parts in the best-of-breed technology solution of the present invention, and the consumption of polyurethane prepolymer (I) is 35～45 weight parts, and polyurethane adhesive is 40～53 weight parts with softening agent, filler and catalyst consumption.
Polyurethane prepolymer described in the technical solution of the present invention (II), it is characterized in that polyether glycol wherein comprises: polyether glycol Tdiol-400 (Tianjin the 3rd petroleum chemical plant, Mn=400, functionality is 2), Tdiol-700 (Tianjin the 3rd petroleum chemical plant, Mn=700, functionality is 2), Tdiol-1000 (Tianjin the 3rd petroleum chemical plant, Mn=1000, functionality is 2), Tdiol-2000 (Tianjin the 3rd petroleum chemical plant, Mn=2000, functionality is 2), TMN-700 (Tianjin the 3rd petroleum chemical plant, Mn=700, functionality is 3), TMN-1000 (Tianjin the 3rd petroleum chemical plant, Mn=1000, functionality is 3), TMN-3000 (Tianjin the 3rd petroleum chemical plant, Mn=3000, functionality is 3), TMN-4000 (Tianjin the 3rd petroleum chemical plant, Mn=4000, functionality is 3), GSE-2028 (Shanghai Gaoqiao petrochemical corporation (complex), Mn=4000, moisture≤0.05%, functionality is 2), GEP-330N (Shanghai Gaoqiao petrochemical corporation (complex), Mn=4800, moisture≤0.05%, functionality is 3), polytetrahydrofuran diol (PTMEG) etc.Consumption is 2%～5%Wt of polyurethane prepolymer (II).
Chainextender in the polyurethane prepolymer described in the technical solution of the present invention (II) can be by making in the following chainextender: polyethylene glycol adipate glycol CMA-244 (Yantai Synthetic Leather Factory, Mn=2000, moisture≤0.03%, functionality is 2), polycaprolactone glycol Tone-1241 (DOW chemical company, Mn=2000, the normal temperature state is a colorless solid, functionality is 2), polycaprolactone glycol Tone-2241 (DOW chemical company, Mn=2000, the normal temperature state is a colorless solid, functionality is 2), polycaprolactone glycol CAPA-2200 (Britain Solvay Interox company, Mn=2000, the normal temperature state is the wax shape, functionality is 2), polycarbonate diol T-5652 (chemical Co., Ltd. of Japanese Asahi Chemical Industry, Mn=2000, the normal temperature state is a thick liquid, functionality is 2), 1,4 butyleneglycols (BDO), ethylene glycol (EG), glycol ether (DEG), N-methyl-monoethanolamine, N, N-dihydroxyl (di-isopropyl) aniline (QL-HPA), two (2-ethyl) ethers (HQEE) of quinhydrones, 1,4-cyclohexanedimethanol (CHDM), two (hydroxyethyl) ethers (HER) of Resorcinol, TriMethylolPropane(TMP) (TMP) etc.Consumption is 45%～50%Wt of polyurethane prepolymer (II).
Isocyanic ester in the polyurethane prepolymer described in the technical solution of the present invention (II) comprises: diphenylmethanediisocyanate (MDI) (Yantai ten thousand magnificent urethane company limited), tolylene diisocyanate (TDI) (Cangzhou, Hebei bigization TDI limited liability company), isoflurane chalcone diisocyanate (IPDI) (Degussa company) etc.Consumption is 8%～15%Wt of polyurethane prepolymer (II).
Thinner comprises in the polyurethane prepolymer described in the technical solution of the present invention (II): solvent xylene, plasticizer DOP (dioctyl phthalate (DOP)).Consumption accounts for 35%～45%Wt of polyurethane prepolymer (II).
Catalyzer comprises in the polyurethane prepolymer described in the technical solution of the present invention (II): dibutyl tin laurate (DBTDL), stannous octoate, dibutyltin diacetate (DBTAC), 2,2-dual-morpholinyl diethyl ether (DMDEE), 1,8-diazacyclo hendecene (DBU) etc.Consumption accounts for 0%～0.05%Wt of polyurethane prepolymer (II).
Polyurethane prepolymer described in the technical solution of the present invention (I), it is characterized in that polyether glycol wherein comprises: polyether glycol Tdiol-400 (Tianjin the 3rd petroleum chemical plant, Mn=400, functionality is 2), Tdiol-700 (Tianjin the 3rd petroleum chemical plant, Mn=700, functionality is 2), Tdiol-1000 (Tianjin the 3rd petroleum chemical plant, Mn=1000, functionality is 2), Tdiol-2000 (Tianjin the 3rd petroleum chemical plant, Mn=2000, functionality is 2), TMN-700 (Tianjin the 3rd petroleum chemical plant, Mn=700, functionality is 3), TMN-1000 (Tianjin the 3rd petroleum chemical plant, Mn=1000, functionality is 3), TMN-3000 (Tianjin the 3rd petroleum chemical plant, Mn=3000, functionality is 3), TMN-4000 (Tianjin the 3rd petroleum chemical plant, Mn=4000, functionality is 3), GSE-2028 (Shanghai Gaoqiao petrochemical corporation (complex), Mn=4000, moisture≤0.05%, functionality is 2), GEP-330N (Shanghai Gaoqiao petrochemical corporation (complex), Mn=4800, moisture≤0.05%, functionality is 3), polytetrahydrofuran diol (PTMEG) etc.Consumption accounts for 2%～5%Wt of polyurethane prepolymer (I).
Chainextender in the polyurethane prepolymer described in the technical solution of the present invention (I) can be by making in the following chainextender: polyethylene glycol adipate glycol CMA-244 (Yantai Synthetic Leather Factory, Mn=2000, moisture≤0.03%, functionality is 2), polycaprolactone glycol Tone-1241 (DOW chemical company, Mn=2000, the normal temperature state is a colorless solid, functionality is 2), polycaprolactone glycol Tone-2241 (DOW chemical company, Mn=2000, the normal temperature state is a colorless solid, functionality is 2), polycaprolactone glycol CAPA-2200 (Britain Solvay Interox company, Mn=2000, the normal temperature state is the wax shape, functionality is 2), polycarbonate diol T-5652 (chemical Co., Ltd. of Japanese Asahi Chemical Industry, Mn=2000, the normal temperature state is a thick liquid, functionality is 2), 1,4 butyleneglycols (BDO), ethylene glycol (EG), glycol ether (DEG), N-methyl-monoethanolamine, N, N-dihydroxyl (di-isopropyl) aniline (QL-HPA), two (2-ethyl) ethers (HQEE) of quinhydrones, 1,4-cyclohexanedimethanol (CHDM), two (hydroxyethyl) ethers (HER) of Resorcinol, TriMethylolPropane(TMP) (TMP) etc.Consumption is 50%～60%Wt of polyurethane prepolymer (I).
Isocyanic ester in the polyurethane prepolymer described in the technical solution of the present invention (I) comprises: diphenylmethanediisocyanate (MDI) (Yantai ten thousand magnificent urethane company limited), tolylene diisocyanate (TDI) (Cangzhou, Hebei bigization TDI limited liability company), isoflurane chalcone diisocyanate (IPDI) (Degussa company) etc.Consumption is 10%～17%Wt of polyurethane prepolymer (I).
Thinner comprises in the polyurethane prepolymer described in the technical solution of the present invention (I): solvent xylene, plasticizer DOP (dioctyl phthalate (DOP)).Consumption is 23%～35%Wt of polyurethane prepolymer (I).
Single component moisture curing high strength polyurethane adhesive of the present invention synthesized molecular weight at 10000～15000 polyurethane prepolymers (II) and molecular weight at 10000～20000 polyurethane prepolymer (I), so the mechanical property of single component moisture curing high strength polyurethane adhesive of the present invention increases substantially, compare with the monocomponent moisture cure urethanes adhesive of prior art, following advantage arranged:
(1) single component moisture curing high strength polyurethane adhesive mechanical property of the present invention increases substantially, and tensile strength reaches 13.3Mpa.
(2) single component moisture curing high strength polyurethane adhesive tear strength of the present invention reaches 54.7KN/m.
(3) single component moisture curing high strength polyurethane adhesive of the present invention has solved the room temperature storage stability problem, and the room temperature storage phase reaches 2 years.Can be used for high-grade automobile loading and maintenance use.
Embodiment
Polyurethane prepolymer (I) synthetic embodiment is as follows:
Polyurethane prepolymer (I)
1The polyether Glycols DL-1000 that adds 512.8g in dry there-necked flask vacuumizes dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, add the thinner dimethylbenzene 202.3g and the diphenylmethanediisocyanate 259.3g that measure, slowly be warmed up to 80 ℃, insulation reaction 3h lowers the temperature 55 ℃ then, adds the chainextender N-methyl monoethanolamine 25.6g that measures, in 80 ℃ of reaction 2～3h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
2The polyether Glycols DL-2000 that adds 77.8g in dry there-necked flask vacuumizes dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, add and measure diphenylmethanediisocyanate 19.4g, slowly be warmed up to 80 ℃, insulation reaction 3h lowers the temperature 55 ℃ then, add the chainextender 1 that measures, 4-cyclohexanedimethanol 2.8g is in 80 ℃ of reaction 2～3h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
3The polyether Glycols DL-1000 that adds 565.7g in dry there-necked flask vacuumizes dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, add and measure diphenylmethanediisocyanate 282.8g and thinner 125.7g, slowly be warmed up to 80 ℃, insulation reaction 3h lowers the temperature 55 ℃ then, adds the chainextender N-methyl monoethanolamine 25.8g that measures, in 80 ℃ of reaction 2～3h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
4The polyether Glycols DL-2000 that adds 709.7g in dry there-necked flask vacuumizes dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, add and measure diphenylmethanediisocyanate 184.5g and thinner 71.0g, slowly be warmed up to 80 ℃, insulation reaction 3h lowers the temperature 55 ℃ then, adds two (hydroxyethyl) ether (HER) 34.8g of the chainextender Resorcinol that measures, in 80 ℃ of reaction 2～3h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
5The polyether Glycols DL-2000 and the 407.2g chainextender polyester polyol 244 that add 407.2g in dry there-necked flask vacuumize dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, add the diphenylmethanediisocyanate 140.3g and the 45.2g thinner dimethylbenzene that measure, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
6In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 71.3g and the chainextender polycaprolactone glycol Tone-1241 of 609.0g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, diphenylmethanediisocyanate 167.5g that adding measures and the thinner dimethylbenzene of 152.3g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
7In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 39.8g and the chainextender polycaprolactone glycol Tone-1241 of 568.2g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, diphenylmethanediisocyanate 164.8g that adding measures and the thinner of 227.2g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
8In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 33.8g and the chainextender polycaprolactone glycol CAPA-2200 of 482.6g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, diphenylmethanediisocyanate 120.8g that adding measures and the thinner of 362.0g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
9In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 37.0g and the chainextender polycaprolactone glycol CAPA-2200 of 529.1g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, diphenylmethanediisocyanate 142.8g that adding measures and the thinner of 291.2g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
10In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 37.0g and the chainextender polycaprolactone glycol CAPA-2200 of 529.1g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, diphenylmethanediisocyanate 152.8g that adding measures and the thinner of 291.2g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
11In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 38.0g and the polyether Glycols DL-2000 of 217.4g and the chainextender polycaprolactone glycol Tone-2241 of 326.1g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, diphenylmethanediisocyanate 146.7g that adding measures and the thinner of 251.8g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (I)
12The polyether-tribasic alcohol TMN-700 of adding 37.2g and the structural formula of the present invention of 670.2g are H-[O-(R in dry there-necked flask
2)
5-CO-] m-O-R
1-O-[CO-(R
2)
5-O] n-NHCO-R
3Chainextender under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, add the thinner of the 292.6g measure, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.R in the chainextender structural formula in the prepolymer wherein
1For-C
2H
4-, R
2For-CH
2-, R
3For containing aromatic NCO compound, m is 9, and n is 8:
H-[O-(CH
2)
5-CO-]
9—O—C
2H
4-O-[CO-(CH
2)
5-O]
8-NHCO-R
3
Polyurethane prepolymer (I)
13The polyether-tribasic alcohol TMN-700 of adding 37.2g and the structural formula of the present invention of 680.2g are H-[O-(R in dry there-necked flask
2)
5-CO-] m-O-R
1-O-[CO-(R
2)
5-O] n-NHCO-R
3Chainextender under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, add the thinner of the 271.7g measure, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.R in the chainextender structural formula in the prepolymer wherein
1For-C
2H
4-, R
2For-CH
2-, R
3For containing aromatic NCO compound, m is 9, and n is 8:
H-[O-(CH
2)
5-CO-]
9—O—CH
2-C(CH
3)
2—CH
2-O-[CO-(CH
2)
5-O]
8-NHCO-R
3
Polyurethane prepolymer (I)
14The polyether-tribasic alcohol GEP-330N that adds 154.0g in dry there-necked flask vacuumizes dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, diphenylmethanediisocyanate 28.4g that adding measures and the thinner of 17.6g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II) synthetic embodiment is as follows:
Polyurethane prepolymer (II)
1The polyether Glycols DL-2000 that adds 769.2g in dry there-necked flask vacuumizes dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, isoflurane chalcone diisocyanate 176.9g that adding measures and the catalyzer dibutyl tin laurate of 0.01g, slowly be warmed up to 80 ℃, insulation reaction 3h lowers the temperature 55 ℃ then, add the chainextender N that measures, N-dihydroxyl (di-isopropyl) aniline 53.8g is in 80 ℃ of reaction 2～3h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II)
2The polyether-tribasic alcohol 330N that adds 878.5g in dry there-necked flask vacuumizes dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, isoflurane chalcone diisocyanate 120.5g that adding measures and the catalyzer dibutyl tin laurate of 1g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II)
3The polyester diol 5652 that adds 812.9g in dry there-necked flask vacuumizes dehydration 0.5～1h under 120 ℃, be cooled to about 60 ℃, isoflurane chalcone diisocyanate 187.0g that adding measures and the catalyzer DMDEE of 0.16g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II)
4In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 72.4g and the chainextender polycaprolactone glycol Tone-1241 of 620.6g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, isoflurane chalcone diisocyanate 145.4g that adding measures and catalyzer dibutyl tin laurate and the thinner 161.6g of 0.2g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II)
5In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 37.8g and the chainextender polycaprolactone glycol Tone-1241 of 504.5g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, isoflurane chalcone diisocyanate 151.3g that adding measures and catalyzer dibutyl tin laurate and the thinner 270.3g of 0.1g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II)
6In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 39.1g and the chainextender polycaprolactone glycol CAPA-2200 of 558.6g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, isoflurane chalcone diisocyanate 182.9g that adding measures and catalyzer dibutyl tin laurate and the thinner 279.3g of 0.16g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II)
7In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 39.1g and the chainextender polycaprolactone glycol CAPA-2200 of 558.6g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, isoflurane chalcone diisocyanate 122.9g that adding measures and catalyzer dibutyl tin laurate and the thinner 279.2g of 0.1g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II)
8In dry there-necked flask, add the polyether-tribasic alcohol TMN-700 of 39.8g and the polyether Glycols DL-2000 of 227.2g and the chainextender polycaprolactone glycol Tone-2241 of 340.9g and under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, isoflurane chalcone diisocyanate 136.3g that adding measures and catalyzer dibutyl tin laurate and the thinner 255.6g of 0.1g, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.
Polyurethane prepolymer (II)
9The polyether-tribasic alcohol TMN-700 of adding 39.1g and the structural formula of the present invention of 681.5g are H-[O-(R in dry there-necked flask
2)
5-CO-] m-O-R
1-O-[CO-(R
2)
5-O] n-NHCO-R
3Chainextender under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, add catalyzer dibutyl tin laurate and the thinner 279.2g of the 0.1g measure, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.R in the chainextender structural formula in the prepolymer wherein
1For-C
2H
4-, R
2For-CH
2-, R
3For containing the NCO compound of ester ring family, m is 9, and n is 8:
H-[O-(CH
2)
5-CO-]
9—O—C
2H
4-O-[CO-(CH
2)
5-O]
8-NHCO-R
3
Polyurethane prepolymer (II)
10The polyether-tribasic alcohol TMN-700 of adding 39.1g and the structural formula of the present invention of 681.9g are H-[O-(R in dry there-necked flask
2)
5-CO-] m-O-R
1-O-[CO-(R
2)
5-O] n-NHCO-R
3Chainextender under 120 ℃, vacuumize dehydration 0.5～1h, be cooled to about 60 ℃, add catalyzer dibutyl tin laurate and the thinner 279.3g of the 0.1g measure, slowly be warmed up to 80 ℃, insulation reaction 3～4h, cooling discharge.Be loaded in the encloses container standby.R in the chainextender structural formula in the prepolymer wherein
1For-CH
2-C (CH
3)
2-CH
2-, R
2For-CH
2-, R
3For containing the NCO compound of ester ring family, m is 9, and n is 8:
H-[O-(CH
2)
5-CO-]
9—O—CH
2-C(CH
3)
2—CH
2-O-[CO-(CH
2)
5-O]
8-NHCO-R
3
The embodiment of joining glue
Joining gluing equipment is: the dynamic mixing homogenizer (special-purpose planetary mixing kettle) that has vacuum unit
The preparation of seal gum: in the dynamic mixing homogenizer, add softening agent, prepolymer etc. in proportion, stir, remove vacuum with drying nitrogen, add after pre-dry filler and catalyzer etc. stir, discharging is put in the sealed vessel with standby, the test physicals.
Produce or pack the worker-house of one-component polyurethane sealant and answer temperature suitable, relative humidity will dehumidify with dehumidifier below 65% in case of necessity.
The physicals test
Seal gum is gluing under room temperature (23 ± 2 ℃, RH55 ± 5%) condition, or make test piece (extrude an amount of polyurethane sealant on the sheet glass that posts PE or PP film, smear into the thick glue-line of 2mm with plaster trowel, not making has bubble in the glue), place after 7 days, test its physicals.
(1) surface drying time: under the standard conditions, on clean sheet glass, extrude about 20g polyurethane sealant sample, smear into the thick sample of 2mm, do not touch sample with clean slick and sly glass stick every 5min with plaster trowel, to seal gum not at sticking glass stick, but the time of glass stick can heave out seal gum the time.
(2) tear strength: carry out (determining sample) with special-purpose cut-off knife by GB/T529.
(3) tensile strength: press GB-528-1998 and carry out.(adopt S2 type paper knife to determine test piece, draw speed is 500mm/min).
(4) elongation at break: press GB-528-1998 and carry out.
(5) trickling property: direction is coated with the sizing material of two φ 10mm in length and breadth in clean test plate (panel) upper edge, erects test plate (panel) with an angle of 90 degrees then, measures adhesive tape mobile distance behind the normality 10min.
Embodiment 1 adds the softening agent of 509.49g and the filler of having dried, polyurethane prepolymer (I) in the dynamic mixing homogenizer
1134.87g, polyurethane prepolymer (I)
14339.66g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 15.98g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 2 adds the softening agent of 509.49g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
1134.87g, polyurethane prepolymer (I)
14339.66g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 15.98g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 3 adds the softening agent of 476.67g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
2101.42g, polyurethane prepolymer (I)
14202.84g and polyurethane prepolymer (I)
3202.84g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.23g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 4 adds the softening agent of 476.67g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
2101.42g, polyurethane prepolymer (I)
14202.84g and polyurethane prepolymer (I)
2202.84g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.23g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 5 adds the softening agent of 476.67g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
2101.42g, polyurethane prepolymer (I)
14202.84g and polyurethane prepolymer (I)
4202.84g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.23g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 6 adds the softening agent of 476.67g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
2101.42g and polyurethane prepolymer (I)
14405.68g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.23g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 7 adds the softening agent of 476.67g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
2101.42g polyurethane prepolymer (I)
14202.84g and polyurethane prepolymer (I)
5152.5g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.23g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Used prepolymer viscosity when joining glue all has increase in various degree among above embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, the embodiment 7, and the viscosity that has is very big, and operability is bad.The glue sample of embodiment is detected by the detection method scraping blade, and performance sees Table one.
Table one
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Tear strength, KN/m | 42.54 | 24.14 | 42.30 | 41.61 | 26.7 | 21.5 | 39 |
| Tensile strength, MPa | 7.91 | 4.74 | 7.32 | 5.55 | 4.4 | 5.6 | 7.55 |
| Elongation at break, % | 457 | 502 | 792 | 788 | 780 | 400 | 715 |
| Trickling property, mm | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Embodiment 8 adds the softening agent of 449.5g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
4152.9g and polyurethane prepolymer (I)
6382.3g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.23g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 9 adds the softening agent of 450.0g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
5153.5g and polyurethane prepolymer (I)
7383.8g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.4g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 10 adds the softening agent of 450.0g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
6153.5g and polyurethane prepolymer (I)
8383.8g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.4g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 11 adds the softening agent of 450.0g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
6153.5g and polyurethane prepolymer (I)
9383.8g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.4g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 12 adds the softening agent of 450.0g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
7153.5g and polyurethane prepolymer (I)
10383.8g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.4g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 13 adds the softening agent of 450.0g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
8153.5g and polyurethane prepolymer (I)
11383.8g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 16.4g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 14 adds the softening agent of 401.5g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
9166.0g and polyurethane prepolymer (I)
12414.8g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 17.7g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Embodiment 15 adds the softening agent of 424.3g and the filler of having dried, polyurethane prepolymer (II) in the dynamic mixing homogenizer
10160.0g and polyurethane prepolymer (I)
13399.8g, vacuumize then and stir, remove vacuum with nitrogen, add other raw materials 17.0g such as catalyzer, vacuumize and stir, discharging is sealed in the aluminum pipe.
Among the above embodiment, except that embodiment 13 tensile strength are slightly little, other embodiment tensile strength all 〉=8Mpa, and there are short problem of shelf lives in embodiment 8, embodiment 9, embodiment 10 and embodiment 11, room temperature is placed and was just occurred viscosity increase, not easy-operating problem in one month; Embodiment 12, embodiment 14 and embodiment 15 intensity all reach requirement, and the shelf lives all can reach 24 months and never degenerate.And the mechanical strength of embodiment 14 is better than embodiment 12 and embodiment 15.The glue sample of embodiment is detected by the detection method scraping blade, and performance sees Table one.
Table two
| Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | |
| Tear strength, KN/m | 65.5 | 71 | 39.36 | 45.4 | 40.07 | 23 | 54.7 | 41.55 |
| Tensile strength, MPa | 14.3 | 14.04 | 10.63 | 9.9 | 8.83 | 3.55 | 13.3 | 9.20 |
| Elongation at break, % | 553 | 635 | 966 | 772 | 550 | 819 | 857 | 620 |
| Trickling property, mm | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Claims (9)
1, a kind of single component moisture curing high strength polyurethane adhesive, it is characterized in that comprising:
(a) 8～20 weight parts are H-[O-(R based on described single component moisture curing high strength polyurethane adhesive by polyether glycol, structural formula
2)
5-CO-] m-O-R
1-O-[CO-(R
2)
5-O] n-NHCO-R
3The polyurethane prepolymer (II) made of chainextender, isocyanic ester, catalyzer, thinner, wherein the consumption of chainextender accounts for 45%～50% He of polyurethane prepolymer (II) consumption
(b) 20～50 weight parts are H-[O-(R based on described single component moisture curing high strength polyurethane adhesive by polyether glycol, structural formula
2)
5-CO-] m-O-R
1-O-[CO-(R
2)
5-O] n-NHCO-R
3The polyurethane prepolymer (I) made of chainextender, isocyanic ester, thinner, wherein the consumption of chainextender accounts for 50%～60% He of polyurethane prepolymer (I) consumption
(c) 30～60 weight parts are based on polyurethane adhesive softening agent, filler and the catalyzer of described single component moisture curing high strength polyurethane adhesive.
2, according to the described single component moisture curing high strength polyurethane adhesive of claim 1, it is characterized in that: wherein the consumption of polyurethane prepolymer (II) is 9～18 weight parts, the consumption of polyurethane prepolymer (I) is 25～48 weight parts, and polyurethane adhesive is 37～55 weight parts with softening agent, filler and catalyst consumption.
3, according to the described single component moisture curing high strength polyurethane adhesive of claim 1, it is characterized in that: wherein the consumption of polyurethane prepolymer (II) is 10～17 weight parts, the consumption of polyurethane prepolymer (I) is 35～45 weight parts, and polyurethane adhesive is 40～53 weight parts with softening agent, filler and catalyst consumption.
4, according to claim 1,2 or 3 described single component moisture curing high strength polyurethane adhesives, it is characterized in that: wherein the polyether glycol consumption is 2～5 weight parts in the polyurethane prepolymer (II), the chainextender consumption is 45～50 weight parts, the isocyanic ester consumption is 8～15 weight parts, the thinner consumption is 35～45 weight parts, and catalyst levels is 0～0.05 weight part.
5, according to claim 1,2 or 3 described single component moisture curing high strength polyurethane adhesives, it is characterized in that: wherein the polyether glycol consumption is 2～5 weight parts in the polyurethane prepolymer (I), the chainextender consumption is 50～60 weight parts, the isocyanic ester consumption is 10～17 weight parts, and the thinner consumption is 23～35 weight parts.
6, require 1,2 or 3 described single component moisture curing high strength polyurethane adhesives according to profit, it is characterized in that: wherein the molecular weight of polyurethane prepolymer (II) is 10000～15000, the molecular weight 10000～20000 of polyurethane prepolymer (I).
7, according to claim 1,2 or 3 described single component moisture curing high strength polyurethane adhesives, it is characterized in that: R in the structural formula of chainextender in the polyurethane prepolymer wherein
1Representative-C
2H
4-or-C
4H
8-or-C
2H
4-O-C
2H
4-or-CH
2-C (CH
3)
2-CH
2-; R
2Representative-CH
2-; R
3Representative contains the compound of NCO group.
8, according to claim 1,2 or 3 described single component moisture curing high strength polyurethane adhesives, it is characterized in that: wherein in the polyurethane prepolymer in the structural formula of chainextender m be 1～30, n is 1～30.
9, according to claim 1,2 or 3 described single component moisture curing high strength polyurethane adhesives, it is characterized in that: the molecular weight M of the chainextender in the polyurethane prepolymer wherein
nBetween 2000～2500.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100537187A CN101418203A (en) | 2007-10-25 | 2007-10-25 | Single component moisture curing high strength polyurethane adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100537187A CN101418203A (en) | 2007-10-25 | 2007-10-25 | Single component moisture curing high strength polyurethane adhesive |
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| CN101418203A true CN101418203A (en) | 2009-04-29 |
Family
ID=40629210
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100537187A Pending CN101418203A (en) | 2007-10-25 | 2007-10-25 | Single component moisture curing high strength polyurethane adhesive |
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| CN102516918A (en) * | 2011-12-14 | 2012-06-27 | 湖北回天胶业股份有限公司 | Dual-component polyurethane adhesive with high elongation rate and preparation method thereof |
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| CN107955576B (en) * | 2017-12-11 | 2021-02-02 | 济南北方泰和新材料有限公司 | High-strength flame-retardant polyurethane sealant for high-speed railway passenger cars and preparation method thereof |
| CN107955576A (en) * | 2017-12-11 | 2018-04-24 | 济南北方泰和新材料有限公司 | High-strength anti-flaming type high-speed track passenger car polyurethane sealant and preparation method thereof |
| WO2020035761A1 (en) * | 2018-08-14 | 2020-02-20 | 3M Innovative Properties Company | Extruded polyurethane surface films |
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Application publication date: 20090429 |