CN114478975B - Curing agent, preparation method thereof and application of curing agent in preparation of polyacrylate pressure-sensitive adhesive - Google Patents
Curing agent, preparation method thereof and application of curing agent in preparation of polyacrylate pressure-sensitive adhesive Download PDFInfo
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- CN114478975B CN114478975B CN202210269038.3A CN202210269038A CN114478975B CN 114478975 B CN114478975 B CN 114478975B CN 202210269038 A CN202210269038 A CN 202210269038A CN 114478975 B CN114478975 B CN 114478975B
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
Abstract
The application relates to a curing agent, a preparation method thereof and application of the curing agent in preparing polyacrylate pressure-sensitive adhesive, wherein the curing agent is diisocyanate blocked oligomer obtained by reacting a compound containing active hydrogen atoms with diisocyanate.
Description
Technical Field
The application relates to the technical field of organic polymers, in particular to a curing agent, a preparation method thereof and application of the curing agent in preparation of polyacrylate pressure-sensitive adhesives.
Background
In month 1 of 2020, the ecological environment department has issued comments about further enhancement of plastic pollution control, and indicates that by the end of 2025, the use of non-degradable plastic tapes is prohibited by the national postal delivery network for the field of plastic packaging for express delivery. Thus, there is a mention of the use of degradable tapes instead of non-degradable plastic tapes in the provinces of related policies.
The polyacrylate pressure-sensitive adhesive tape has the advantages of high adhesive strength, excellent weather resistance, good low-temperature performance and the like as the most commonly used adhesive tape at present, and has very wide application. However, since the main bond of acrylic ester is a stable C-C skeleton, degradation performance is poor, degradation can be achieved only by modification, and researchers usually introduce degradable groups such as benzyl pyridinium groups, diterpenoid compounds, polylactic acid, polycaprolactone, natural polymers/compounds and the like into chain segments of acrylic ester adhesives to improve biodegradability, but industrialization is not achieved at present. The reason is that the original process is affected by the preparation of the polyacrylate pressure-sensitive adhesive in the mode, for example, the process conditions such as temperature, reaction time, catalyst, pretreatment and post-treatment in the synthesis process are required to be changed, so that the research and development test cost is greatly increased, and the excellent adhesive performance cannot be ensured. Therefore, it is considered to improve the biodegradability of the adhesive tape from the way of modifying the curing agent.
The commonly used curing agents include isocyanates, epoxy resins and metal chelates, wherein the isocyanates have the advantages of high curing agent activity, low curing temperature, stable performance after curing and the like, and become the most widely applied curing agents. However, the conventional isocyanate curing agent has smaller molecular weight, and the prepared adhesive has fewer degradable parts and poor degradability when the addition amount of the curing agent is smaller, and if the addition amount of the curing agent is greatly increased in order to improve the biodegradability of the pressure-sensitive adhesive, the crosslinking degree is too high, so that the finally prepared pressure-sensitive adhesive has large hardness and poor adhesive property and cannot be used.
Disclosure of Invention
The first technical problem to be solved by the present application is to provide a curing agent with higher molecular weight, excellent biodegradability and high curing activity, aiming at the current state of the art.
The second technical problem to be solved by the application is to provide a preparation method of the curing agent aiming at the current state of the art.
The third technical problem to be solved by the application is to provide an application of the curing agent in preparing polyacrylate pressure-sensitive adhesive aiming at the current state of the art.
In order to solve the first technical problem, the application adopts the following technical scheme: a curing agent, characterized in that: the curing agent is diisocyanate blocked oligomer obtained by reacting a compound containing active hydrogen atoms with diisocyanate.
The isocyanate groups are readily reactive with compounds containing active hydrogen atoms, such as amines, water, alcohols, acids, bases, and the like. In order to keep the solidifying activity of isocyanate, the isocyanate can be reacted with biodegradable polyalcohol, polycarboxylic acid, polyamine and other compounds to prepare the oligomer with the main chain containing abundant hydrolyzable groups and biodegradable groups and the tail end of isocyanate groups. Among them, the biodegradable polyols are preferred glycerides of fatty acids, including glyceryl stearate, glyceryl oleate, glyceryl ricinoleate (i.e., castor oil), etc., the biodegradable polycarboxylic acids are preferred carboxyl-terminated dimer polyesters or trimer polyesters, such as butylene succinate and butylene adipate dimers and trimers, etc., and the biodegradable polyamines are preferred amino acid glycerides, such as glycine glyceride, glutamic acid glyceride, etc. At present, the degradable polyol, the polybasic carboxylic acid and the polybasic amine compound can be used for preparing products such as polyurethane, polyamide and the like, so that the compound containing active hydrogen atoms is preferably selected from at least one of polybasic amine, polyhydric alcohol and polybasic carboxylic acid.
Preferably, the compound containing active hydrogen atoms is at least one of polyamines, polyols and polycarboxylic acids containing ester bonds.
In the above embodiment, preferably, the polyhydric alcohol is a fatty acid glyceride.
Preferably, the polyalcohol is at least one of glyceryl monostearate, glycerol monooleate and castor oil.
Preferably, the polyamine is selected from at least one of glycine glyceride and glutamic acid glyceride; the polycarboxylic acid is selected from at least one of butanediol/succinic acid dimer and butanediol/adipic acid dimer.
Preferably, the oligomers have a number average molecular weight in the range 1,500 to 25,000Da. When the number average molecular weight is too high, i.e., the content of the reactive isocyanate groups is too low, the amount of the active ingredient is too small in the case of the same proportion of the curing agent to be added, resulting in substantially no crosslinking effect. However, after the reactive isocyanate group content exceeds a certain amount (for example, 0.08 mmol/g), the degree of crosslinking increases, and as the reactive isocyanate group content continues to increase, the degree of crosslinking gradually increases. However, when the content of the reactive isocyanate groups exceeds 1.4mmol/g, the crosslinking degree is too high, which tends to cause a significant decrease in the performance of the prepared pressure-sensitive adhesive. Therefore, it is recommended that the curing agent has a number average molecular weight of between 1,500 and 25,000Da.
Preferably, the diisocyanate is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
In order to solve the second technical problem, the application adopts the following technical scheme: the preparation method of the curing agent is characterized by comprising the following steps:
(1) Sequentially adding a compound containing active hydrogen atoms and diisocyanate into a reaction container, stirring and reacting for 2-4 hours under the condition of 55-75 ℃ in a nitrogen atmosphere, wherein the molar ratio of the compound containing active hydrogen atoms to the diisocyanate is 0.9-1.1, and forming a mixed solution I;
(2) Adding a solvent (such as ethyl acetate) into the first mixed solution, uniformly stirring at normal temperature, pouring into a closed container, and storing at 0-5 ℃ for standby use to obtain a second mixed solution, wherein the second mixed solution is a curing agent solution;
(3) And taking a part of the mixed solution II, measuring the content of the active isocyanate groups by using a di-n-butylamine titration method, and calculating the number average molecular weight of the curing agent.
In the above scheme, in the step (3), the di-n-butylamine titration method is specifically as follows: and (3) reacting the mixed solution II with excessive di-n-butylamine solution, adding 1-2 drops of indicator (bromocresol green solution), titrating the mixed solution II with hydrochloric acid aqueous alcohol solution until the indicator changes from blue or purple to yellow, recording the volume of consumed hydrochloric acid aqueous alcohol solution, titrating the same hydrochloric acid aqueous alcohol solution with the di-n-butylamine solution until the indicator changes from blue or purple to yellow, recording the volume of consumed hydrochloric acid aqueous alcohol solution, converting the difference of the volumes of the two consumed hydrochloric acid aqueous alcohol solutions to obtain the content of active isocyanate groups in the curing agent, and further calculating the number average molecular weight of the curing agent according to the content of the active isocyanate groups.
In order to solve the third technical problem, the technical scheme adopted by the application is as follows: the application of the curing agent in preparing polyacrylate pressure-sensitive adhesive.
Preferably, the polyacrylate pressure-sensitive adhesive is prepared from a curing agent and an acrylic ester adhesive, wherein the mass ratio of the acrylic ester adhesive to the curing agent is (5-7) (3-5), so that the phenomenon of cross-linking does not occur, and the pressure-sensitive adhesive can be ensured to have good biodegradability.
Compared with the prior art, the application has the advantages that: the molecular weight (1,500-25,000 Da) of the curing agent is higher than that of the common curing agent, so that the dosage of the acrylic adhesive for preparing the pressure-sensitive adhesive can be correspondingly reduced, and the curing agent with the content of 30 percent or more is added into the acrylic adhesive, so that obvious cross-linking phenomenon can not occur; in addition, the curing activity of the curing agent is equivalent to that of the common curing agent, and the curing agent can realize the low-temperature and high-temperature curing.
In addition, the curing agent disclosed by the application contains a plurality of hydrolyzable groups, the hydrolyzed substances are easy to degrade in a manner of oxidative decarboxylation and the like, and then the hydrolyzed substances are introduced into the adhesive, so that the prepared pressure-sensitive adhesive has high corresponding components of the curing agent and more hydrolyzable groups, and the final biodegradability is good.
Furthermore, the mode of preparing the pressure-sensitive adhesive by adopting the curing agent disclosed by the application can not only not increase the cost burden excessively, but also keep the performance of the original polyacrylate pressure-sensitive adhesive as much as possible, and the pressure-sensitive adhesive production process is not required to be additionally improved, and the existing pressure-sensitive adhesive production process is adopted, so that the cost is low and the applicability is wide.
Drawings
FIG. 1 is an infrared spectrum of the curing agent of example 11 of the present application.
Detailed Description
The application is described in further detail below in connection with specific examples.
The following are structural formulas of reactant 1 and reactant 2 in table one.
Table one example and comparative example
All chemicals in the table above were purchased from Shanghai Alasdine Biotechnology Co.
Molar ratio of monomers: molar ratio of isocyanate to active hydrogen atom-containing Compound
In the above table, reactant 1 is a compound containing an active hydrogen atom, and reactant 2 is a diisocyanate, specifically as follows:
MG: glyceryl monostearate
OG: glycerol monooleate
CO: castor oil
BS: butanediol/succinic acid dimer
BA: butanediol/adipic acid dimer
GG: glycine glyceride
GAG: glycerol glutamate
TDI: toluene diisocyanate
MDI: diphenylmethane diisocyanate
HDI: hexamethylene diisocyanate
The preparation methods of each example and comparative example in the above table are:
(1) Sequentially adding a compound containing active hydrogen atoms and diisocyanate into a reaction container (such as a four-neck flask) according to the monomer mole ratio in the table, stirring for reaction under the condition of introducing nitrogen according to the reaction temperature and the reaction time in the table, wherein the stirring speed is 200r/min, and forming a mixed solution I;
(2) Adding ethyl acetate into the first mixed solution, wherein the adding amount of the ethyl acetate is the same as the total mass of the first mixed solution, uniformly stirring at normal temperature, pouring into a closed container (such as a sealable glass bottle), stirring at the speed of 200r/min, and storing at the temperature of 0-5 ℃ for later use to obtain a second mixed solution;
(3) And taking a part of the mixed solution II, measuring the content of the active isocyanate groups by using a di-n-butylamine titration method, and calculating the number average molecular weight of the curing agent.
The di-n-butylamine titration method is specifically as follows: and (3) reacting the mixed solution II with excessive di-n-butylamine solution, adding 1-2 drops of indicator (bromocresol green solution), titrating the mixed solution II with hydrochloric acid aqueous alcohol solution until the indicator changes from blue or purple to yellow, recording the volume of consumed hydrochloric acid aqueous alcohol solution, titrating the same hydrochloric acid aqueous alcohol solution with the di-n-butylamine solution until the indicator changes from blue or purple to yellow, recording the volume of consumed hydrochloric acid aqueous alcohol solution, converting the difference of the volumes of the two consumed hydrochloric acid aqueous alcohol solutions to obtain the content of active isocyanate groups in the curing agent, and further calculating the number average molecular weight of the curing agent according to the content of the active isocyanate groups. Wherein bromocresol green solution is 0.04% bromocresol green in 50% ethanol, di-n-butylamine solution is di-n-butylamine toluene solution, prepared by mixing 150mL di-n-butylamine and 450mL toluene, aqueous hydrochloric acid alcoholic solution is prepared by mixing 50mL concentrated hydrochloric acid (36.0-38.0 wt.%) and 450mL absolute ethanol, and 0.3mol/L Na is used 2 CO 3 The aqueous solution is calibrated.
As shown in Table one, the present application includes 18 examples and 6 comparative examples. The types of reactants added, amounts of reactants added, and the isocyanate group reactive content of the reaction product and corresponding converted number average molecular weights for each example are set forth in Table one. It can be seen from the table that the isocyanate and the polyol, polycarboxylic acid or polyamine containing an ester bond can react under the above conditions, and the curing agent having different crosslinking activities is produced according to the reaction conditions, and when the temperature is too high, the curing agent itself is crosslinked, the reaction is insufficient due to too high a molar ratio, too low a temperature or too short a reaction time, and the curing activity is lost due to too long a reaction time or too small a molar ratio.
Taking the curing agent of example 11, removing the solvent, and measuring the infrared spectrum of the product, which is 1400-2500 cm -1 The graph is shown in FIG. 1, from which it can be seen that the curve is 1520cm -1 And 1702cm -1 The peak is shown, which belongs to N-H bending vibration peak and vibration peak of carbonyl in urethane, namely, the characteristic peak of-NH-COO-, and indicates that the carbamate substance is prepared by reaction. At the same time, the curve is 2270cm -1 The peak is shown, which belongs to the characteristic peak of-N=C=O bond, and shows that isocyanate groups are still reserved in the product, so that the product has certain curing activity.
Placing a certain mass part of acrylic adhesive (SK-1717 DT manufactured by Zodiac chemical Co., ltd., of course, other acrylic adhesives manufactured by the inventor) into a beaker, adding curing agent solutions with different active isocyanate group contents, rapidly stirring for 10min to obtain a mixture, coating the mixture on release paper, drying at 80 ℃ to remove solvent in reactants (curing agent and adhesive), and curing in a baking oven at 40 ℃ for at least 2 days. After completion of curing, it was immersed in ethyl acetate for at least 2 days, and the mass difference before and after washing and drying was measured to calculate the degree of crosslinking (mass after immersion/mass before immersion), and the results are shown in Table II.
Crosslinking degree of pressure-sensitive adhesive prepared by curing agents with different reactive isocyanate group contents
As shown in the table, the crosslinking degree of the reactive isocyanate group is continuously increased along with the increase of the content of the reactive isocyanate group or the increase of the use amount of the curing agent, which indicates that the curing agent has curing effect on the acrylic adhesive and the curing effect is adjustable. When the content of the reactive isocyanate groups is too low (i.e., the molecular weight is too large), the reactive component is too small in the same proportion of the curing agent to be added, resulting in substantially no crosslinking effect. However, after the reactive isocyanate group content exceeds a certain amount (for example, 0.08 mmol/g), the degree of crosslinking increases, and as the reactive isocyanate group content continues to increase, the degree of crosslinking gradually increases. However, when the content of the reactive isocyanate groups exceeds 1.4mmol/g, the crosslinking degree is too high, which tends to cause a significant decrease in the properties of the pressure-sensitive adhesive produced. Therefore, it is recommended that the number average molecular weight of the curing agent is between 1,500 and 25,000Da, if a high amount of curing agent is required (for example greater than 50%), it is recommended that the molecular weight is between 5,000 and 25,000Da.
Claims (4)
1. The application of a curing agent in preparing polyacrylate pressure-sensitive adhesive is characterized in that: the curing agent is diisocyanate blocked oligomer obtained by reacting a compound containing active hydrogen atoms with diisocyanate; the compound containing active hydrogen atoms is at least one of glycin glyceride and glutamic acid glyceride; the number average molecular weight of the oligomer ranges from 1,500 Da to 25,000Da;
the preparation method of the curing agent comprises the following steps:
(1) Sequentially adding a compound containing active hydrogen atoms and diisocyanate into a reaction container, stirring and reacting for 2-4 hours under the condition of 55-75 ℃ in a nitrogen atmosphere, wherein the molar ratio of the compound containing active hydrogen atoms to the diisocyanate is 0.9-1.1, and forming a mixed solution I;
(2) Adding a solvent into the first mixed solution, uniformly stirring at normal temperature, pouring into a closed container, and storing at 0-5 ℃ for later use to obtain a second mixed solution;
(3) And taking a part of the mixed solution II, measuring the content of the active isocyanate groups by using a di-n-butylamine titration method, and calculating the number average molecular weight of the curing agent.
2. The application of the curing agent in preparing polyacrylate pressure-sensitive adhesive according to claim 1, which is characterized in that: the diisocyanate is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
3. The application of the curing agent in preparing polyacrylate pressure-sensitive adhesive according to claim 1, which is characterized in that: in the step (3), the di-n-butylamine titration method is specifically as follows: and (3) reacting the mixed solution II with excessive di-n-butylamine solution, adding an indicator, titrating the mixed solution II with hydrochloric acid aqueous alcohol solution until the indicator turns from blue or purple to yellow, recording the volume of the consumed hydrochloric acid aqueous alcohol solution, titrating the same hydrochloric acid aqueous alcohol solution with the di-n-butylamine solution until the indicator turns from blue or purple to yellow, recording the volume of the consumed hydrochloric acid aqueous alcohol solution, converting the difference of the volumes of the two consumed hydrochloric acid aqueous alcohol solutions to obtain the content of active isocyanate groups in the curing agent, and further calculating the number average molecular weight of the curing agent according to the content of the active isocyanate groups.
4. The application of the curing agent in preparing polyacrylate pressure-sensitive adhesive according to claim 1, which is characterized in that: the polyacrylate pressure-sensitive adhesive is prepared from a curing agent and an acrylic adhesive, wherein the mass ratio of the acrylic adhesive to the curing agent is (5-7) and (3-5).
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| CN202210269038.3A CN114478975B (en) | 2022-03-18 | 2022-03-18 | Curing agent, preparation method thereof and application of curing agent in preparation of polyacrylate pressure-sensitive adhesive |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340682A (en) * | 1981-05-07 | 1982-07-20 | Synthetic Surfaces, Inc. | Adhesive consisting essentially of an isocyanate terminated ricinoleate prepolymer and a chlorinated polyvinyl chloride |
| JP2001131513A (en) * | 1999-11-04 | 2001-05-15 | Ipposha Oil Ind Co Ltd | Pressure-sensitive adhesive and adhered article |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340682A (en) * | 1981-05-07 | 1982-07-20 | Synthetic Surfaces, Inc. | Adhesive consisting essentially of an isocyanate terminated ricinoleate prepolymer and a chlorinated polyvinyl chloride |
| US4340682B1 (en) * | 1981-05-07 | 1986-04-01 | ||
| JP2001131513A (en) * | 1999-11-04 | 2001-05-15 | Ipposha Oil Ind Co Ltd | Pressure-sensitive adhesive and adhered article |
Non-Patent Citations (1)
| Title |
|---|
| 新型生物降解交联剂的制备和交联壳聚糖的性能;杨媛;罗丙红;周长忍;;材料研究学报(第01期);第25-31页 * |
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