CN108203502B - Water-soluble cross-linking agent and application thereof in water-based resin - Google Patents
Water-soluble cross-linking agent and application thereof in water-based resin Download PDFInfo
- Publication number
- CN108203502B CN108203502B CN201810038489.XA CN201810038489A CN108203502B CN 108203502 B CN108203502 B CN 108203502B CN 201810038489 A CN201810038489 A CN 201810038489A CN 108203502 B CN108203502 B CN 108203502B
- Authority
- CN
- China
- Prior art keywords
- water
- soluble
- linking agent
- structural formula
- chemical structural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/06—Epoxy-capping
- C08G2650/08—Epoxy- capping used as a source of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a water-soluble cross-linking agent and application thereof in water-based resin, wherein the water-soluble cross-linking agent is prepared by carrying out chemical reaction on 1,3, 5-tris (epoxypropyl) isocyanurate and hydrophilic substances in a reaction kettle to obtain water-soluble isocyanurate containing a diepoxy group. The isocyanurate is added into the common water-based resin, and crosslinking is realized through the reaction of a diepoxy group in the isocyanurate and a group of hydroxyl and carboxyl in the water-based resin, so that the comprehensive performance of the common water-based resin is greatly improved.
Description
Technical Field
The present invention relates to a crosslinking agent, and more particularly, to a crosslinking agent applied to an aqueous resin.
Background
The aqueous resin is a novel resin system using water as a dispersion medium instead of an organic solvent. And fusing with water to form a solution, and forming a resin film material after the water is volatilized. The aqueous resin is not an aqueous resin per se, but a film material obtained after water is volatilized is required.
The cross-linking agent is a substance which can play a bridging role between linear molecules, so that a plurality of linear molecules are mutually bonded and cross-linked to form a net structure. A substance that promotes or regulates the formation of covalent or ionic bonds between polymer molecular chains.
With the stricter and stricter environmental protection requirements, the demand of people on water-based environment-friendly products is more and more urgent no matter in daily life or industrial production, and the water-based modification of the products is more and more trend in the fields of adhesives, coatings, printing ink and the like.
In order to improve the overall performance of the aqueous resin, for example: cohesive strength, water resistance, heat resistance, weather resistance, hardness, etc., and usually need to be modified by adding an appropriate crosslinking agent. The existing crosslinking agent has the defects of high organic volatile, poor stability, temporary addition before use and the like. Therefore, the development of a low-volatile, storage-stable water-soluble crosslinking agent is of particular novel and innovative interest.
Disclosure of Invention
The invention aims to provide a water-soluble cross-linking agent, which is prepared by adding 100g of 1,3, 5-tris (epoxypropyl) isocyanurate (TGIC) and 30-250 g of hydrophilic substance with a chemical structural formula I into a reaction kettle, uniformly stirring, heating to 95-100 ℃, carrying out heat preservation reaction for 2 hours, cooling to below 40 ℃, adding 130-350 g of water, uniformly stirring and discharging.
The invention also provides a method for applying the water-soluble dual-epoxy-group-containing isocyanurate to the common water-based resin, and the dual-epoxy group in the isocyanurate reacts with the hydroxyl, carboxyl and other groups in the water-based resin to realize crosslinking, so that the water resistance, heat resistance, weather resistance, hardness and other properties of the common water-based resin are greatly improved.
The preparation method of the water-soluble cross-linking agent is characterized by comprising the following steps: adding 100g of 1,3, 5-tris (epoxypropyl) isocyanurate (TGIC) and 30-250 g of hydrophilic substance with a chemical structural formula I into a reaction kettle, uniformly stirring, heating at a heating rate of 1-5 ℃/min, reacting at a temperature of 95-100 ℃ for 2-10 hours, cooling to below 40 ℃, adding 130-350 g of purified water, uniformly stirring, and discharging to obtain a water-soluble cross-linking agent; the chemical structural formula of the water-soluble cross-linking agent is as follows:
the hydrophilic substance with the chemical structural formula I is as follows:
in the chemical structural formula I, R1Represents hydrogen (H) or methyl (CH 3).
The water-soluble cross-linking agent has the advantages that:
① the water-soluble cross-linking agent can be synthesized, non-volatile, stable and completely water-soluble by controlling the reaction temperature and the synthesis time, and avoids the existence of volatile organic compounds in the water-soluble cross-linking agent.
② the water-soluble cross-linking agent of the invention is mixed with the common water-based resin, and the diepoxy group in the cross-linking agent is cross-linked with the hydroxyl and/or carboxyl in the water-based resin, so that the comprehensive performances of the common water-based resin such as water resistance, heat resistance, weather resistance, hardness, cohesive strength and the like can be greatly improved.
③ the water-soluble cross-linking agent has stable water-soluble characteristic, can be directly added into common water-based resin for long-term storage, and avoids various defects of the two-component cross-linking agent in use.
Detailed Description
The present invention will be described in further detail with reference to examples.
The invention relates to a water-soluble cross-linking agent, which is prepared by adding 100g of 1,3, 5-tris (epoxypropyl) isocyanurate (TGIC) and 30-250 g of hydrophilic substance with a chemical structural formula I into a reaction kettle, uniformly stirring, heating to 95-100 ℃, reacting for 2-10 hours under heat preservation, then cooling to below 40 ℃, adding 130-350 g of purified water, uniformly stirring, and discharging.
The chemical structural formula of the water-soluble cross-linking agent is as follows:
the chemical structural formula I is as follows:
in the chemical structural formula I, R1Represents hydrogen (H) or methyl (CH 3).
In the present invention, the water-soluble crosslinking agent is a water-soluble, diepoxy group-containing isocyanurate.
Example 1
Adding 297 g of 1,3, 5-tris (epoxypropyl) isocyanurate (TGIC) and 646 g of Octylphenol Polyoxyethylene Ether (OPE) into a reaction kettle, uniformly stirring, heating at the heating rate of 5 ℃/min, reacting for 2 hours at the temperature of 95 ℃, then cooling to 35 ℃, adding 943 g of purified water, uniformly stirring, and discharging to obtain the water-soluble cross-linking agent.
100g of the water-soluble crosslinking agent obtained in example 1 was added to 1500 g of the aqueous acrylic resin, and the mixture was stirred uniformly to obtain an aqueous acrylic modified resin. And then coating the water-based acrylic modified resin on a glass substrate with the thickness of 2 mm, and naturally drying to obtain the water-based acrylic modified resin emulsion film.
Coating the traditional water-based acrylic resin on a glass substrate with the thickness of 2 mm, and naturally drying to obtain the water-based acrylic resin emulsion film.
Table 1 shows the results of the performance test of the latex film obtained in example 1 of the present invention. Wherein the water resistance is determined according to the specification of GB/T1733 + 1993 and the immersion test method (A method), and the immersion is carried out for 10 hours. The solvent resistance was measured by the manual wiping method (method A) as specified in GB/T23989-. Tensile strength samples were prepared according to GB/T528-2009, tensile speed 100mm/min, tensile load 250N.
TABLE 1
In the invention, the diepoxy group in the water-soluble cross-linking agent prepared in the embodiment 1 reacts with the hydroxyl group, the carboxyl group and other groups in the water-based acrylic resin to realize cross-linking, so that the comprehensive performance of the water-based acrylic modified resin is greatly improved.
Example 2
Adding 297 g of 1,3, 5-tris (epoxypropyl) isocyanurate (TGIC) and 660 g of Nonylphenol Polyoxyethylene Ether (NPE) into a reaction kettle, uniformly stirring, heating at a heating rate of 10 ℃/min, reacting for 2 hours at a temperature of 100 ℃, then cooling to 40 ℃, adding 957g of water, uniformly stirring, and discharging to obtain the water-soluble cross-linking agent.
100g of the water-soluble crosslinking agent obtained in example 2 was added to 1500 g of the aqueous acrylic resin, and the mixture was stirred uniformly to obtain an aqueous acrylic modified resin. And then coating the water-based acrylic modified resin on a glass substrate with the thickness of 2 mm, and naturally drying to obtain the water-based acrylic modified resin emulsion film.
Coating the traditional water-based acrylic resin on a glass substrate with the thickness of 2 mm, and naturally drying to obtain the water-based acrylic resin emulsion film.
Table 2 shows the results of the performance test of the latex film obtained in example 2 of the present invention. Wherein the water resistance is determined according to the specification of GB/T1733 + 1993 and the immersion test method (A method), and the immersion is carried out for 10 hours. The solvent resistance was measured by the manual wiping method (method A) as specified in GB/T23989-. Tensile strength samples were prepared according to GB/T528-2009, tensile speed 100mm/min, tensile load 250N.
TABLE 2
Adding 297 g of 1,3, 5-tris (epoxypropyl) isocyanurate (TGIC) and 178 g of triethylene glycol monoethyl ether into a reaction kettle, uniformly stirring, heating at the heating rate of 8 ℃/min, keeping the temperature for reaction for 2.5 hours after heating to 95 ℃, then cooling to 30 ℃, adding 475g of water, uniformly stirring, and discharging to obtain the water-soluble cross-linking agent.
100g of the water-soluble crosslinking agent obtained in example 3 was added to 1500 g of the aqueous acrylic resin, and the mixture was stirred uniformly to obtain an aqueous acrylic modified resin. And then coating the water-based acrylic modified resin on a glass substrate with the thickness of 2 mm, and naturally drying to obtain the water-based acrylic modified resin emulsion film.
Coating the traditional water-based acrylic resin on a glass substrate with the thickness of 2 mm, and naturally drying to obtain the water-based acrylic resin emulsion film.
Table 3 shows the results of the performance test of the latex film obtained in example 3 of the present invention. Wherein the water resistance is determined according to the specification of GB/T1733 + 1993 and the immersion test method (A method), and the immersion is carried out for 10 hours. The solvent resistance was measured by the manual wiping method (method A) as specified in GB/T23989-. Tensile strength samples were prepared according to GB/T528-2009, tensile speed 100mm/min, tensile load 250N.
TABLE 3
Claims (5)
1. A method for preparing aqueous polymer emulsion containing water-soluble cross-linking agent is characterized in that: the aqueous polymer emulsion contains one or two of hydroxyl and/or carboxyl groups, and 100g of aqueous acrylic resin contains 1-10 g of water-soluble cross-linking agent;
adding 100g of 1,3, 5-tris (epoxypropyl) isocyanurate and 30-250 g of hydrophilic substance with a chemical structural formula I into a reaction kettle, uniformly stirring, heating at a heating rate of 1-5 ℃/min, reacting at a temperature of 95-100 ℃ for 2-10 hours in a heat preservation manner, then cooling to below 40 ℃, adding 130-350 g of purified water, uniformly stirring, and discharging to obtain the water-soluble cross-linking agent;
the water-soluble cross-linking agent is water-soluble isocyanurate containing a diepoxy group;
the chemical structural formula of the water-soluble cross-linking agent is as follows:
the hydrophilic substance with the chemical structural formula I is as follows:
said R represents hydrogen (H) or
Or
said m represents
The number of the repeating units is a natural number between 0 and 100;
in the chemical structural formula I, R1Represents hydrogen (H) or methyl (CH)3）。
2. The method for preparing an aqueous polymer emulsion containing a water-soluble crosslinking agent according to claim 1, wherein: the chemical structural formula I is octyl phenol polyoxyethylene ether.
3. The method for preparing an aqueous polymer emulsion containing a water-soluble crosslinking agent according to claim 1, wherein: the chemical structural formula I is nonylphenol polyoxyethylene ether.
4. The method for preparing an aqueous polymer emulsion containing a water-soluble crosslinking agent according to claim 1, wherein: the chemical structural formula I is triethylene glycol monoethyl ether.
5. The method for producing a film by drying the aqueous polymer emulsion containing a water-soluble crosslinking agent according to claim 1, wherein: coating the glass substrate with the thickness of 2 mm, and naturally drying to obtain a film; the cohesive strength of the film is improved by 5-15% compared with the traditional waterborne acrylic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810038489.XA CN108203502B (en) | 2018-01-13 | 2018-01-13 | Water-soluble cross-linking agent and application thereof in water-based resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810038489.XA CN108203502B (en) | 2018-01-13 | 2018-01-13 | Water-soluble cross-linking agent and application thereof in water-based resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108203502A CN108203502A (en) | 2018-06-26 |
| CN108203502B true CN108203502B (en) | 2020-04-21 |
Family
ID=62605592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810038489.XA Active CN108203502B (en) | 2018-01-13 | 2018-01-13 | Water-soluble cross-linking agent and application thereof in water-based resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108203502B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT371816B (en) * | 1979-10-08 | 1983-08-10 | Henkel Kgaa | METHOD FOR PRODUCING NEW ISOCYANURS [UREDERIVATIVES |
| JPH02279684A (en) * | 1989-04-19 | 1990-11-15 | Nissan Chem Ind Ltd | Production of isocyanuric acid derivative |
| CN1257435C (en) * | 2001-04-10 | 2006-05-24 | 日产化学工业株式会社 | Composition for forming antireflection film for lithography |
-
2018
- 2018-01-13 CN CN201810038489.XA patent/CN108203502B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108203502A (en) | 2018-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103694892B (en) | A kind of fluorinated polysiloxane parting agent and preparation method thereof | |
| CN110330881B (en) | Photocuring environment-friendly flexible PVC stain-resistant matte finish paint and preparation method thereof | |
| CN104497330B (en) | Preparation method of photo-crosslinking polyvinyl alcohol/cellulose nanocrystal (PVA/CNC) composite film | |
| CN109868084B (en) | UV polymerization type POSS modified acrylate pressure-sensitive adhesive and preparation method thereof | |
| CN105175687A (en) | Preparation method of zero-VOC (volatile organic compound) high-toughness water-based epoxy resin curing agent | |
| CN115677913A (en) | Organic silicon modified water-soluble acrylic resin, preparation method thereof and environment-friendly water-based varnish for photovoltaic glass glaze | |
| CN109694639B (en) | Water-based glass baking paint and preparation method thereof | |
| CN108546485B (en) | High-solid-content organic-inorganic hybrid resin and preparation method thereof | |
| CN111253837B (en) | Water-based one-coating UV (ultraviolet) curing epoxy acrylate coating and preparation method thereof | |
| CN104497341B (en) | A kind of preparation method of photo crosslinked polyethylene alcohol/lignin PVA/lignin composite membranes | |
| CN113501967B (en) | Supermolecule polymer and preparation method and application thereof | |
| CN103666241B (en) | A kind of composite Nano waterborne UV coating and preparation method thereof | |
| CN107735455B (en) | Fast setting coating compositions having low pH stability and water resistance | |
| CN108203502B (en) | Water-soluble cross-linking agent and application thereof in water-based resin | |
| KR20160097829A (en) | A epoxy adhesive composition comprising poly-thiolhardner and manufacturetingmthetod of it | |
| CN102212309B (en) | Method for preparing unsaturated polyester polyurethane block copolymer solventless coating | |
| CN102627938B (en) | Preparation method of nonsaturated polyester polyurethane segmented copolymer solvent-free adhesive | |
| CN110105902B (en) | Multipurpose high-solid-content double-component composite adhesive and preparation method and application thereof | |
| CN109280154B (en) | Self-emulsifying water-based low-temperature epoxy resin curing agent based on heterocyclic compound | |
| CN114213918A (en) | Water-based wood clear primer and preparation method thereof | |
| CN109456727B (en) | Green light-cured STPU resin and preparation method and application thereof | |
| KR20220046402A (en) | Composition for flexible coating film with high surface hardness and method of forming coating film using the same | |
| CN114702878B (en) | High-temperature-resistant epoxy resin composition and application thereof | |
| CN117447909B (en) | Moisture curing type anti-corrosion coating for wind and rain roof and preparation method thereof | |
| CN117069918B (en) | Modified acrylic resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |