CN117757403A - Multicomponent polyurethane rubber product repair adhesive and preparation method and application thereof - Google Patents
Multicomponent polyurethane rubber product repair adhesive and preparation method and application thereof Download PDFInfo
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- CN117757403A CN117757403A CN202211127289.4A CN202211127289A CN117757403A CN 117757403 A CN117757403 A CN 117757403A CN 202211127289 A CN202211127289 A CN 202211127289A CN 117757403 A CN117757403 A CN 117757403A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 43
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 43
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 27
- 230000008439 repair process Effects 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title abstract description 7
- -1 diamine compound Chemical class 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 235000013877 carbamide Nutrition 0.000 claims abstract description 9
- 229920001971 elastomer Polymers 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 43
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229920002635 polyurethane Polymers 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000013530 defoamer Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 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 6
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 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 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- JTBAOJVLBMPVBV-UHFFFAOYSA-N [2,4-diamino-5-methyl-3-(sulfanylmethyl)phenyl]methanethiol Chemical compound CC1=CC(CS)=C(N)C(CS)=C1N JTBAOJVLBMPVBV-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- XIUZJXMFUSKNNX-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trione;urea Chemical compound NC(N)=O.O=C1NC(=O)NC(=O)N1 XIUZJXMFUSKNNX-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003678 scratch resistant effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 238000004090 dissolution Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000000126 substance Substances 0.000 description 13
- 239000004970 Chain extender Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 11
- 238000004321 preservation Methods 0.000 description 11
- 239000003292 glue Substances 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 241001112258 Moca Species 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229950009390 symclosene Drugs 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a multi-component polyurethane rubber product repairing adhesive, a preparation method and application thereof, and relates to the technical field of adhesives, wherein the repairing adhesive comprises a component A, a component B and a component C; the component A comprises isocyanate and polyalcohol; the component B comprises a small molecular diamine compound, a solvent B, a defoaming agent and a catalyst; the component C comprises carbamide isocyanate and a solvent C; the component A comprises the following components in parts by weight: 100 parts by weight of isocyanate; 140-400 parts by weight of polyalcohol; the component B comprises the following components in parts by weight: 25-40 parts by weight of small molecular diamine compound; 100 parts by weight of a solvent B; 0.03-0.1 part by weight of a defoaming agent; 0.03-0.1 part by weight of a catalyst; the component C comprises the following components in parts by weight: 1-10 parts by weight of carbamide isocyanate; 100 parts by weight of a C solvent. The repairing adhesive is cured Wen Yuan, the surface of the adhesive conveyor belt is not fallen off after the adhesive solution is cured, and the repairing adhesive is wear-resistant and scratch-resistant.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a multi-component polyurethane rubber product repairing adhesive, a preparation method and application thereof.
Background
The rubber conveyer belt has excellent wear resistance, burning resistance, cold resistance and other characteristics, and is widely used in mining industry, metallurgy industry and the like. However, the tensile body (metal or fabric) of the conveyer belt is exposed as the conveyer belt is used for a long time or is impacted by minerals to cause abrasion or damage, so that the use safety of the conveyer belt is affected, and the whole conveyer belt is possibly replaced when the conveyer belt is seriously used, so that the replacement cost is high and the shutdown loss is caused. In order to make the conveyer belt continue to be used as soon as possible, repair methods such as a patch repair method and a mechanical clamping method are generally adopted in early stages, but the repair effect of these methods is generally not ideal.
Along with the invention and development of the adhesive, the adhesive is widely applied to various industries, the repair of the rubber conveyer belt is also listed, the repair adhesive for the rubber conveyer belt is also generated, and the adhesive is favored because the adhesive has the advantages of high repair speed, strong performance, easy preservation and the like.
Compared with other common repairing rubber materials, the polyurethane has the advantages of excellent fatigue resistance, wide curing temperature range, wide application range, outstanding low temperature resistance, convenient use and easy preservation, is suitable for quickly repairing the rubber conveyer belt under the working condition, so that polyurethane is usually selected as the main component of the rubber repairing rubber, and meanwhile, the relevant adjustment and control of the curing time and other performances are realized by correspondingly adding auxiliary agents such as a defoaming agent, a catalyst and the like.
At present, related researches and reports on polyurethane repairing adhesives exist, related products are also known, but the polyurethane repairing adhesives have poor mechanical properties, low adhesive strength to rubber, poor wear resistance and difficult curing speed to meet the operation of actual working conditions.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a multi-component polyurethane rubber product repairing adhesive, and a preparation method and application thereof. The repair adhesive of the invention cures Wen Yuan: the curing rate is proper at the temperature of-10 ℃ to 30 ℃ so as to ensure the operable time; the performance is excellent: the surface of the adhesive conveyor belt is not fallen off after the adhesive solution is solidified, and the adhesive conveyor belt is wear-resistant and scratch-resistant; the use is convenient: the coating is carried out after blending and stirring at room temperature, and heating or ultraviolet irradiation is not needed; low toxicity and environmental protection: the toxicity of the raw materials is low, and the human health of a user is not damaged; easy preservation: the chemical property is mild, and the product can be stored for several months at normal temperature.
One of the purposes of the invention is to provide a multi-component polyurethane rubber product repairing adhesive, which comprises an A component, a B component and a C component;
the component A comprises isocyanate and polyalcohol;
the component B comprises a small molecular diamine compound, a solvent B, a defoaming agent and a catalyst;
the component C comprises carbamide isocyanate and a solvent C;
the component A comprises the following components in parts by weight:
100 parts by weight of isocyanate;
140-400 parts by weight of polyalcohol;
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
1-20 parts by weight of carbamide isocyanate;
100 parts by weight of a C solvent.
Preferably, the component A comprises the following components in parts by weight:
100 parts by weight of isocyanate;
170-300 parts by weight of polyalcohol;
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
3-10 parts by weight of carbamide isocyanate;
100 parts by weight of a C solvent.
Preferably, the mass ratio of the A, B components is 100: (30-130), preferably 100: (40-100); the dosage of the component C is 2-20 mu L/cm of the surface of the rubber product 2 Preferably 6-10. Mu.L/cm 2 。
Preferably, the isocyanate in the component A is at least one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate;
the molecular weight of the polyalcohol in the component A is 850-2000; the polyalcohol is polyether glycol or polyester glycol; preferably at least one of polyethylene glycol, polypropylene glycol, polycaprolactone diol and polytetrahydrofuran diol.
Preferably, the small molecular diamine compound in the component B is at least one of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, ethylenediamine, polyetheramine, piperazine, 2, 4-diamino-3, 5-dimethyl-thiotoluene;
the solvent B in the component B is at least one of tetrahydrofuran, acetone, methyl ethyl ketone and ethyl acetate;
at least one of an antifoaming agent, namely an organosilicon antifoaming agent or a polyether antifoaming agent in the component B;
the catalyst in the component B is at least one of an organotin catalyst, an organic amine catalyst and a polyurethane JFH type catalyst.
Preferably, the isocyanuric acid urea in the component C is at least one of trichloroisocyanuric acid urea, dichloro isocyanuric acid urea, dibromoisocyanuric acid urea and tribromoisocyanuric acid urea;
the C solvent in the component C is at least one of tetrahydrofuran, acetone, methyl ethyl ketone and ethyl acetate.
The formula of the invention can also be added with conventional auxiliary agents according to actual conditions, such as carbon black, gas-phase white carbon black and nano CaCO in the component A 3 The conventional auxiliary agents are added to achieve the reinforcing effect, the wear resistance can be enhanced within a certain range, the shrinkage rate of the rubber can be reduced, and meanwhile, the production cost can be reduced.
The second object of the invention is to provide a preparation method of the multi-component polyurethane rubber product repair adhesive, which comprises the following steps:
stirring and prepolymerizing the component A according to the weight parts to obtain the component A;
stirring and mixing the components of the component B according to the weight parts to obtain the component B;
and stirring and mixing the components of the component C according to the weight parts to obtain the component C.
Preferably, the stirring pre-polymerization is carried out under protective gas, the reaction temperature is 80-90 ℃, and the reaction time is 1.5-2h.
Preferably, the component A is subjected to vacuum defoaming treatment after stirring and prepolymerization, the rotating speed of a stirring paddle is adjusted to be 50-60rad/min, the vacuum degree is 0.08-0.10MPa, and the defoaming time is 10-20min.
The following scheme can be adopted specifically:
the synthesis of the component A is a prepolymerization process, wherein the polyol is added into a three-neck flask, the rotating speed of a stirring paddle is adjusted to 100-150rad/min, the temperature is controlled to 105-120 ℃, the dehydration is carried out for 2-2.5h under the vacuum condition that the vacuum degree is 0.09MPa, the temperature is reduced to 55-60 ℃, the vacuumizing is stopped, the nitrogen is introduced, the isocyanate is metered and added, the temperature is increased to 80-90 ℃, the reaction is carried out for 1.5-2h, the temperature is reduced to room temperature, and the sealed preservation is carried out in the nitrogen atmosphere to prevent the moisture from entering and causing deterioration;
the component B is a chain extender component, a small molecular diamine compound is added into a sample bottle, a metered solvent B is added, magnetic stirring is carried out, a defoaming agent and a catalyst are sequentially added after complete dissolution, magnetic stirring is continued, stirring is stopped after complete dissolution, and nitrogen is introduced as protection gas seal for storage;
the component C is a rubber surface chemical treating agent, carbamide isocyanate is added into a sample bottle, a metered solvent C is added, magnetic stirring is carried out, stirring is stopped after complete dissolution, and nitrogen is introduced as protection gas for hermetic sealing and storage.
The invention further provides an application of the multi-component polyurethane rubber product repairing adhesive in a rubber product repairing process, wherein the component C is coated on the surface of a rubber product to be repaired, and then the component A and the component B are mixed and coated on the component C.
The following scheme can be adopted specifically:
a, B components are mixed according to the mass ratio of 100: the main components of the polyurethane repairing adhesive are prepared by mixing the components (30-130) at room temperature, and the polyurethane repairing adhesive is used by matching with the component C, is applied to the rapid repair of the worn part of a conveyer belt or a rubber product at room temperature, and can be used for polishing the surface of the rubber product to be repaired by 60-mesh sand paper before repairing.
The preparation process is simple, the component A is simply synthesized, and the component B, C is stirred and mixed; the arrangement of multiple components improves the stability of each component and is convenient for the storage of the repair adhesive; an operator can adjust the mixing amount of A, B components according to actual needs, so that the curing time is mastered, and the actual application under the working condition is satisfied; the component A is viscous, the viscosity is greatly reduced after the component B is mixed, the viscosity adjusting range in the curing process is wide, and the component C can improve the adhesive strength of the repair adhesive to the rubber surface.
The invention has the following beneficial effects:
1) Curing Wen Yuan: the curing rate is proper at the temperature of-10 ℃ to 30 ℃ so as to ensure the operable time;
2) The performance is excellent: the surface of the adhesive conveyor belt is not fallen off after the adhesive solution is solidified, and the adhesive conveyor belt is wear-resistant and scratch-resistant;
3) The use is convenient: the coating is carried out after blending and stirring at room temperature, and heating or ultraviolet irradiation is not needed;
4) Low toxicity and environmental protection: the toxicity of the raw materials is low, and the human health of a user is not damaged;
5) Easy preservation: the chemical property is mild, and the product can be stored for several months at normal temperature.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the examples of the invention are all commercial products, and the specific information is shown in Table 1:
TABLE 1
Example 1
(1) 250 parts by weight of polytetrahydrofuran glycol (PTMG Mn=1000) is added into a three-neck flask, the rotation speed of a stirring paddle is adjusted to 100rad/min, the temperature is controlled to 115 ℃, the vacuum degree is 0.09MPa, the dehydration is carried out for 2 hours, the temperature is reduced to 55 ℃, the vacuumizing is stopped, nitrogen is introduced, 100 parts by weight of diphenylmethane diisocyanate (MDI) is metered and added, the rotation speed of the stirring paddle is adjusted to 350rad/min, the temperature is increased to 80 ℃, the reaction is carried out for 2 hours, the temperature is reduced to room temperature, the vacuum defoaming is carried out, the vacuum degree is set to 0.08MPa, the vacuum defoaming time is 10 minutes, the vacuum is released and the product is taken out, and the product is sealed and stored in a nitrogen atmosphere, thus obtaining the A component prepolymer.
(2) 30 parts by weight of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA) is added into a sample bottle, 100 parts by weight of ethyl acetate is added, magnetic stirring is performed, 0.05 part by weight of organosilicon defoamer AT-720T and 0.05 part by weight of JSFH-02 type polyurethane catalyst are sequentially added after complete dissolution, magnetic stirring is continued, stirring is stopped after complete dissolution, nitrogen is introduced as a protective airtight seal for storage, and the component B chain extender is prepared.
(3) 10 parts by weight of trichloroisocyanuric acid is added into a sample bottle, 100 parts by weight of tetrahydrofuran is added, magnetic stirring is carried out, stirring is stopped after complete dissolution, nitrogen is introduced as protection gas seal for preservation, and the C-component rubber surface chemical treating agent is prepared.
(4) The C component rubber surface chemical treating agent is uniformly smeared on the rubber surface to be repaired, and the dosage is 8 mu L/cm 2 After the liquid is completely evaporated, mixing the A-component prepolymer and the B-component chain extender according to the mass ratio of 100:76, bonding rubber, pouring the glue solution into a mold, curing at room temperature for 7 days to obtain the polyurethane elastomer, and performing performance test.
Example 2
(1) 170 parts by weight of polytetrahydrofuran glycol (PTMG Mn=850) is added into a three-neck flask, the rotation speed of a stirring paddle is adjusted to 100rad/min, the temperature is controlled to 115 ℃, the dehydration is carried out for 2 hours under the vacuum condition of 0.09MPa, the temperature is reduced to 55 ℃, the vacuumizing is stopped, nitrogen is introduced, 100 parts by weight of Toluene Diisocyanate (TDI) is metered and added, the rotation speed of the stirring paddle is adjusted to 350rad/min, the temperature is increased to 85 ℃, the temperature is reduced to room temperature, the vacuum defoaming is carried out, the vacuum degree is set to 0.08MPa, the vacuum defoaming time is 15 minutes, the vacuum is released after the defoaming, the product is taken out, and the product is hermetically stored in the nitrogen atmosphere, so that the component A prepolymer is prepared.
(2) Adding 30 parts by weight of 4,4' -diaminodiphenylmethane (DDM) into a sample bottle, adding 100 parts by weight of ethyl acetate, magnetically stirring, sequentially adding 0.01 part by weight of organosilicon defoamer AT-720T and 0.01 part by weight of JSFH-02 type polyurethane catalyst after complete dissolution, magnetically stirring, stopping stirring after complete dissolution, and introducing nitrogen for preserving as a protective airtight seal to prepare the component B chain extender.
(3) 15 parts by weight of trichloroisocyanuric acid urea is added into a sample bottle, 100 parts by weight of ethyl acetate is added, magnetic stirring is carried out, stirring is stopped after complete dissolution, nitrogen is introduced as protection gas seal for preservation, and the C-component rubber surface chemical treating agent is prepared.
(4) The C component rubber surface chemical treating agent is uniformly smeared on the rubber surface to be repaired, and the dosage is 6 mu L/cm 2 After the liquid is completely evaporated, mixing the prepolymer of the A component and the chain extender of the B component according to the mass ratio of 100:85, bonding rubber, pouring the glue solution into a mold, curing for 7 days at room temperature, and obtaining the polyurethane elastomer for performance test.
Example 3
(1) 240 parts by weight of polypropylene glycol (PPG mn=1000) is added into a three-neck flask, the rotation speed of a stirring paddle is adjusted to 100rad/min, the temperature is controlled to 115 ℃, the dehydration is carried out for 2 hours under the vacuum condition that the vacuum degree is 0.09MPa, the temperature is reduced to 55 ℃, the vacuumizing is stopped, nitrogen is introduced, 100 parts by weight of Toluene Diisocyanate (TDI) is metered and added, the rotation speed of the stirring paddle is adjusted to 350rad/min, the temperature is increased to 85 ℃, the reaction is carried out for 2 hours, the temperature is reduced to room temperature, the vacuum defoaming is carried out, the vacuum defoaming time is set to 0.10MPa, the vacuum is released after the defoaming, the foam is taken out, and the product is hermetically stored in the nitrogen atmosphere, so that the component a prepolymer is prepared.
(2) Adding 30 parts by weight of 2, 4-diamino-3, 5-dimethyl-thiotoluene (DMTDA) into a sample bottle, adding 100 parts by weight of ethyl acetate, magnetically stirring, sequentially adding 0.20 part by weight of an organosilicon defoamer AT-619 and 0.20 part by weight of a JSFH-01 polyurethane catalyst after complete dissolution, magnetically stirring, stopping stirring after complete dissolution, and introducing nitrogen as a protective airtight seal for preservation, thereby obtaining the component B chain extender.
(3) Adding 20 parts by weight of trichloroisocyanuric acid into a sample bottle, adding 100 parts by weight of acetone, magnetically stirring, stopping stirring after complete dissolution, and introducing nitrogen for airtight preservation under protection to obtain the component C rubber surface chemical treatment agent.
(4) The C component rubber surface chemical treating agent is uniformly smeared on the rubber surface to be repaired, and the dosage is 10 mu L/cm 2 After the liquid is completely evaporated, mixing the prepolymer of the A component and the chain extender of the B component according to the mass ratio of 100:54, bonding rubber, pouring the glue solution into a mold, curing for 7 days at room temperature, and obtaining the polyurethane elastomer for performance test.
Example 4
(1) 400 parts by weight of polycaprolactone diol (PCL Mn=2000) was added into a three-neck flask, the rotational speed of a stirring paddle was adjusted to 100rad/min, the temperature was controlled to 115 ℃, the vacuum degree was 0.09MPa, the dehydration was performed for 2 hours, the temperature was reduced to 55 ℃, the evacuation was stopped, nitrogen was introduced, 100 parts by weight of Hexamethylene Diisocyanate (HDI) was metered and added, the rotational speed of the stirring paddle was adjusted to 350rad/min, the temperature was increased to 90 ℃, the reaction was performed for 1.5 hours, the temperature was reduced to room temperature, the vacuum was defoamed, the vacuum degree was set to 0.09MPa, the vacuum was removed for 15 minutes after the defoamation, and the mixture was stored in a sealed manner in a nitrogen atmosphere, thereby obtaining the A-component prepolymer.
(2) 35 parts by weight of 2, 4-diamino-3, 5-dimethyl thiotoluene (DMTDA) is added into a sample bottle, 100 parts by weight of methyl ethyl ketone is added, magnetic stirring is carried out, 0.10 part by weight of polyether defoamer DT-650 and 0.10 part by weight of dibutyltin dilaurate catalyst are sequentially added after complete dissolution, magnetic stirring is continued, stirring is stopped after complete dissolution, nitrogen is introduced as a protection airtight seal for storage, and the component B chain extender is prepared.
(3) Adding 1 part by weight of dichloroisocyanuric acid into a sample bottle, adding 100 parts by weight of tetrahydrofuran, magnetically stirring, stopping stirring after complete dissolution, and introducing nitrogen for airtight preservation, thereby preparing the C-component rubber surface chemical treating agent.
(4) The C component rubber surface chemical treating agent is uniformly smeared on the rubber surface to be repaired, and the dosage is 12 mu L/cm 2 After the liquid is completely evaporated, mixing the A-component prepolymer and the B-component chain extender according to the mass ratio of 100:40, bonding rubber, pouring the glue solution into a mold, and curing for 7 days at room temperature to obtain the polyurethane foamTo polyurethane elastomers, performance testing was performed.
Example 5
(1) 140 parts by weight of polycaprolactone diol (pclmn=1000) is added into a three-neck flask, the rotation speed of a stirring paddle is adjusted to 100rad/min, the temperature is controlled to 115 ℃, the vacuum degree is 0.09MPa, the dehydration is carried out for 2 hours, the temperature is reduced to 55 ℃, the vacuumizing is stopped, nitrogen is introduced, 100 parts by weight of diphenylmethane diisocyanate (MDI) is metered and added, the rotation speed of the stirring paddle is adjusted to 350rad/min, the temperature is increased to 90 ℃, the reaction is carried out for 1.7 hours, the temperature is reduced to room temperature, the vacuum defoaming is carried out, the vacuum degree is set to 0.09MPa, the defoaming time is 20 minutes, the vacuum is released and the product is taken out, and the product is sealed and stored in a nitrogen atmosphere, thus obtaining the component a prepolymer.
(2) 40 parts by weight of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA) is added into a sample bottle, 100 parts by weight of tetrahydrofuran is added, magnetic stirring is performed, 0.15 part by weight of polyether defoamer DT-650 and 0.15 part by weight of dibutyltin dilaurate catalyst are sequentially added after complete dissolution, magnetic stirring is continued, stirring is stopped after complete dissolution, nitrogen is introduced as a protective airtight seal for storage, and the component B chain extender is prepared.
(3) Adding 5 parts by weight of dibromo-isocyanuric acid urea into a sample bottle, adding 100 parts by weight of tetrahydrofuran, magnetically stirring, stopping stirring after complete dissolution, and introducing nitrogen for airtight preservation, thereby preparing the C-component rubber surface chemical treating agent.
(4) The C component rubber surface chemical treating agent is uniformly smeared on the rubber surface to be repaired, and the dosage is 15 mu L/cm 2 After the liquid is completely evaporated, mixing the prepolymer of the A component and the chain extender of the B component according to the mass ratio of 100:115, bonding rubber, pouring the glue solution into a mold, curing for 7 days at room temperature, and obtaining the polyurethane elastomer for performance test.
The multi-component rubber product quick repair adhesive and the commercial constant brand repair adhesive obtained in examples 1-5 were subjected to performance test. Wherein, tensile strength: according to the standard GB/T528-2009, an INSTRON-1121 type material testing machine is adopted to measure the tensile property of the polyurethane elastomer, the spline gauge length is 10mm, the tensile rate is 100mm/min, and 5 parallel splines are taken from each group; adhesive strength: uniformly coating the mixed polyurethane glue solution on the surface of a natural rubber sheet subjected to surface treatment by using the component C, and testing initial peeling force and peeling strength by using a tensile testing machine according to GBT2791-1995, wherein the loading speed of the testing machine is 100mm/min, and the peeling strength is in units of N/mm or kN/m; hardness testing: the hardness of the polyurethane elastomer is tested according to the standard GB/T2411-2008; DIN abrasion test: the abrasion resistance of polyurethane elastomers was characterized by the rotary drum abrasion machine method according to standard GB/T9867-2008.
Aiming at commercial constant brand repairing glue, C component solvent is used for dissolving and smearing C component powder on the surface of 25 mm-100 mm-2.5 mm natural rubber sheet to serve as a rubber matrix, AB components are fully mixed according to the proportion, the rubber matrix is glued, and after the mixed polyurethane glue solution is cured at room temperature, a polyurethane elastomer is obtained and used for testing, and the testing result is shown in table 2.
TABLE 2
As can be seen from the comparative ingredients in the examples, the addition and the addition amount of the different ingredients affect different performances, and the conventional repair requirements of rubber products such as rubber conveyor belts meet the performance indexes of quick room temperature curing, long operation time, firm adhesion, excellent tensile property, wear resistance, hardness suitability and the like.
Claims (10)
1. A multi-component polyurethane rubber product repair adhesive is characterized in that: the repair adhesive comprises a component A, a component B and a component C;
the component A comprises isocyanate and polyalcohol;
the component B comprises a small molecular diamine compound, a solvent B, a defoaming agent and a catalyst;
the component C comprises carbamide isocyanate and a solvent C;
the component A comprises the following components in parts by weight:
100 parts by weight of isocyanate;
140-400 parts by weight of polyalcohol;
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
1-20 parts by weight of carbamide isocyanate;
100 parts by weight of a C solvent.
2. The multi-component polyurethane rubber product repair gel of claim 1, wherein:
the component A comprises the following components in parts by weight:
100 parts by weight of isocyanate;
170-300 parts by weight of polyalcohol;
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
3-10 parts by weight of carbamide isocyanate;
100 parts by weight of a C solvent.
3. The multi-component polyurethane rubber product repair gel of claim 1, wherein: A. the mass ratio of the component B is 100: (30-130), preferably 100: (40-100); the dosage of the component C is 2-20 mu L/cm of the surface of the rubber product 2 Preferably 6-10. Mu.L/cm 2 。
4. The multi-component polyurethane rubber product repair gel of claim 1, wherein: the isocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate;
the molecular weight of the polyalcohol is 850-2000; the polyalcohol is polyether glycol or polyester glycol; preferably at least one of polyethylene glycol, polypropylene glycol, polycaprolactone diol and polytetrahydrofuran diol.
5. The multi-component polyurethane rubber product repair gel of claim 1, wherein: the small molecular diamine compound is at least one of 3,3 '-dichloro-4, 4' -diaminodiphenyl methane, ethylenediamine, polyetheramine, piperazine and 2, 4-diamino-3, 5-dimethyl-thiotoluene;
the solvent B is at least one of tetrahydrofuran, acetone, methyl ethyl ketone and ethyl acetate;
at least one of the defoamer, namely the organosilicon defoamer or the polyether defoamer;
the catalyst is at least one of an organotin catalyst, an organic amine catalyst and a polyurethane JFH type catalyst.
6. The multi-component polyurethane rubber product repair gel of claim 1, wherein: the isocyanuric acid urea is at least one of trichloroisocyanuric acid urea, dichloro isocyanuric acid urea, dibromoisocyanuric acid urea and tribromoisocyanuric acid urea;
the C solvent is at least one of tetrahydrofuran, acetone, methyl ethyl ketone and ethyl acetate.
7. A method for preparing the repair adhesive for multi-component polyurethane rubber products as claimed in any one of claims 1 to 6, characterized in that: the method comprises the following steps:
stirring and prepolymerizing the component A according to the weight parts to obtain the component A;
stirring and mixing the components of the component B according to the weight parts to obtain the component B;
and stirring and mixing the components of the component C according to the weight parts to obtain the component C.
8. The method for preparing the multi-component polyurethane rubber product repair adhesive according to claim 7, wherein the method comprises the following steps: the stirring prepolymerization is carried out under protective gas, the reaction temperature is 80-90 ℃, and the reaction time is 1.5-2h.
9. The method for preparing the multi-component polyurethane rubber product repair adhesive according to claim 7, wherein the method comprises the following steps: and (3) carrying out vacuum defoaming treatment on the component A after stirring and prepolymerization, wherein the vacuum degree is 0.08-0.10MPa, and the defoaming time is 10-20min.
10. Use of a multi-component polyurethane rubber article repair gel according to any one of claims 1-6 in the repair of rubber articles, characterized in that: the component C is coated on the surface of the rubber product to be repaired, and then the component A and the component B are mixed and coated on the component C.
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