CN110951202B - Production process of environment-friendly polyester tile based on rag - Google Patents
Production process of environment-friendly polyester tile based on rag Download PDFInfo
- Publication number
- CN110951202B CN110951202B CN201911274266.4A CN201911274266A CN110951202B CN 110951202 B CN110951202 B CN 110951202B CN 201911274266 A CN201911274266 A CN 201911274266A CN 110951202 B CN110951202 B CN 110951202B
- Authority
- CN
- China
- Prior art keywords
- stirring
- polyester resin
- cotton cloth
- tile
- glass fiber
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
- D06M11/60—Ammonia as a gas or in solution
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a production process of an environment-friendly polyester tile based on broken cloth, which comprises the following specific process steps: adding the high-toughness polyester resin into ethanol, stirring and dissolving to form a glue solution, then adding the hydrophobic cotton cloth, the glass fiber reinforced material, the foaming agent, the release agent and the curing agent, stirring and mixing for 8-10min, then pouring the obtained mixed glue solution into a mold, foaming and curing at 170 ℃ for 30min, cooling and demolding to obtain the environment-friendly polyester tile. According to the invention, the branched unsaturated polyester resin is prepared, and then the modifier is grafted on the molecular chain of the branched unsaturated polyester resin, so that the prepared polyester resin has higher ageing resistance, and the prepared polyester tile has longer service life, thereby solving the problems that the existing polyester resin has low toughness, poor chemical medium resistance and poor water resistance, and the prepared resin tile is easy to age due to long-term irradiation under ultraviolet rays, so that the performance of the resin tile is reduced, and the service life is short.
Description
Technical Field
The invention belongs to the field of polyester tile production, and relates to an environment-friendly polyester tile production process based on rags.
Background
The resin tile is widely applied due to the properties of light weight, corrosion resistance and the like, the polyester resin is widely applied to the preparation of the polyester tile due to the fact that a cured glue line of the polyester resin is high in hardness, good in transparency, high in brightness, capable of being rapidly cured by pressurization at room temperature and good in heat resistance, but the existing polyester resin is not high in toughness, poor in chemical medium resistance and poor in water resistance, and meanwhile, the prepared resin tile is easy to age due to the fact that the prepared resin tile is irradiated under ultraviolet rays for a long time, and the performance of the resin tile is further reduced.
The invention patent with the application number of CN201110251553.0 discloses a straw fiber reinforced polyester tile and a manufacturing method thereof, the polyester tile prepared by compounding straw fibers and m-phenyl polyester resin has good heat preservation, heat insulation and sound insulation performances and a thermal expansion cracking prevention effect, but the heat preservation performance is still low, and the m-phenyl polyester resin used by the straw fiber reinforced polyester tile is easy to age to cause the cracking of the polyester tile after being used for a long time.
Disclosure of Invention
The invention aims to provide a production process of an environment-friendly polyester tile based on rag, which comprises the steps of preparing branched unsaturated polyester resin, and grafting a modifier on a molecular chain of the branched unsaturated polyester resin, so that a large number of phenolic hydroxyl groups are introduced into the prepared polyester resin, wherein the ortho positions of the phenolic hydroxyl groups contain carbonyl groups, intramolecular hydrogen bonds are formed between the phenolic hydroxyl groups and the carbonyl groups to form a six-membered ring structure, the ring structure is closed under normal conditions, the hydrogen bonds are broken after ultraviolet irradiation to release energy, the energy is converted into heat energy after the ultraviolet irradiation, the ultraviolet absorption is realized, the ageing resistance is further realized, the polyester resin has higher ageing resistance, the prepared polyester tile has higher service life, and the problems that the toughness of the existing polyester resin is not high, the chemical medium resistance and the water resistance are poor, and the performance of the resin tile is reduced and the service life is short due to the fact that the prepared resin tile is easy to age under the ultraviolet irradiation for a long time are solved.
The purpose of the invention can be realized by the following technical scheme:
an environment-friendly polyester tile production process based on rag comprises the following specific process steps:
firstly, crushing cotton cloth, adding the crushed cotton cloth into a stirring kettle, adding a 35% sodium hydroxide solution into the stirring kettle, cooking for 4-5 hours at 70-80 ℃, filtering, washing and drying to obtain pretreated cotton cloth, wherein 2.3-2.4L of the 35% sodium hydroxide solution is added into each kilogram of cotton cloth, ester groups on the surface of the cotton cloth can be removed under the action of sodium hydroxide, and then hydroxyl groups on the surface of the cotton cloth are exposed;
secondly, weighing a certain amount of ammonia water and epoxy chloropropane, simultaneously adding the ammonia water and the epoxy chloropropane into a reaction container, heating to 50-60 ℃, stirring for reaction for 5-6h, then adding pretreated cotton cloth and sodium hydroxide into the reaction container, heating to 100-110 ℃, performing reflux reaction for 13-14h, filtering, washing and drying to obtain aminated cotton cloth; ammonia water and epoxy chloropropane according to the mass ratio of 1:1, simultaneously adding 0.11-0.12mol of epoxy chloropropane and 0.06g of sodium hydroxide into every 10 g of pretreated cotton cloth, wherein primary alcohol groups on the cotton fibers can perform substitution reaction with alkyl chloride, so that amino groups are grafted on the cotton fibers, and the cotton fibers still contain secondary hydroxyl groups;
thirdly, adding the aminated cotton cloth into ethanol, uniformly stirring, adding (3-epoxypropylpropoxy) trimethoxy silane, heating to 40-50 ℃, stirring and reacting for 6-7 hours to obtain hydrophobic cotton cloth; wherein 0.12-0.13g of (3-epoxypropylpropoxy) trimethoxy silane is added into each gram of aminated cotton cloth; amino contained in the aminated cotton cloth can react with an epoxy group in the (3-epoxypropylpropoxy) trimethoxy silane, so that a large number of oxysilane bonds are introduced to the surface of the cotton fiber, and the hydrophobic property of the cotton fiber is improved;
fourthly, adding the high-toughness polyester resin into ethanol, stirring and dissolving to form glue solution, then adding hydrophobic cotton cloth, glass fiber reinforced materials, foaming agents, release agents and curing agents into the glue solution, stirring and mixing for 8-10min, then pouring the obtained mixed glue solution into a mold, foaming and curing for 30min at 170 ℃, cooling and demolding to obtain the environment-friendly polyester tile; the high-toughness polyester resin foaming agent comprises hydrophobic cotton cloth, high-toughness polyester resin, a glass fiber reinforced material, a foaming agent, a release agent and a curing agent according to the mass ratio of 100:96-107:19-23:2.4-2.5:3.9-4.2:1.8-1.9, wherein the foaming agent is sodium bicarbonate and foaming agent AC according to the mass ratio of 1:1, and the curing agent is one or more of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate; the high-toughness polyester resin is of a tree-shaped hyperbranched structure, so that the pretreated cotton cloth and the glass fiber reinforced material can be uniformly mixed after being added, meanwhile, the high-toughness polyester resin contains a large amount of carboxyl which can react with epoxy groups in the glass fiber reinforced material, so that the glass fiber reinforced material is grafted on a high-toughness polyester resin chain, the performance of the prepared material is uniform and stable, isocyanate can react with secondary hydroxyl on the surface of the cotton cloth and carboxyl on the polyester resin chain, so that the cotton cloth is uniformly cured in the material, meanwhile, because the cotton cloth and the glass fiber reinforced material are uniformly dispersed in the polyester tile, the surfaces of the cotton cloth and the glass fiber reinforced material both contain oxysilane bonds, so that the prepared polyester tile has high hydrophobic performance, and the prepared polyester tile has high hydrophobic performance, so that the phenomenon that the polyester tile is prevented from water absorption, impregnation and corrosion or water leakage of the polyester tile are effectively avoided;
the specific preparation process of the high-toughness polyester resin is as follows:
step 1: adding diethanolamine into water, stirring and mixing uniformly, adding ethylene glycol diglycidyl ether, heating to 60-70 ℃, stirring and reacting for 2-3h, and then carrying out reduced pressure distillation to obtain a branched polyhydroxy modifier, wherein the reaction structural formula is as follows, and the mass ratio of the diethanolamine to the ethylene glycol diglycidyl ether is 1:1, mixing and adding;
step 2: weighing a certain amount of branched polyhydroxy modifier, adding the branched polyhydroxy modifier into water, heating to 240-250 ℃, adding p-toluenesulfonic acid, stirring for reaction for 10min, adding maleic anhydride, carrying out constant-temperature reflux reaction for 10-12h, and then evaporating to obtain branched unsaturated polyester resin; 0.21-0.23g of maleic anhydride and 0.08g of p-toluenesulfonic acid are added into each gram of branched polyhydroxy modifier, two ends of the branched polyhydroxy modifier contain three hydroxyl groups which are connected through N atoms, the three groups connected through the N atoms are in three different directions of a triangular cone, and the three hydroxyl groups at the two ends are crosslinked with the maleic anhydride and react in three different directions to form a hyperbranched structure, so that the solubility of the branched unsaturated polyester resin is improved, and each crosslinked monomer branched polyhydroxy modifier contains long-chain flexible ether bonds, and a tree-shaped structure chain formed after polymerization is formed by alternately connecting a long-chain flexible ether bond structure and an unsaturated double bond structure, so that the toughness and compatibility of the branched unsaturated polyester resin are greatly improved, and the compatibility between the polyester resin and cloth and glass fiber reinforced materials can be greatly enhanced;
and 3, step 3: adding 2, 4-hexadienoic acid and sodium ethoxide into acetone, stirring and dissolving, then adding o-hydroxyacetophenone into the acetone, stirring and mixing the mixture at normal temperature for reaction for 4 to 5 hours, then evaporating the mixture to remove the solvent, and adding the product into water for recrystallization to obtain a grafting modifier, wherein the reaction structural formula is shown as follows; the ratio of the 2, 4-hexadienoic acid to the o-hydroxyacetophenone is 1:1, adding 8.7-9.2g of sodium ethoxide into each mole of 2, 4-hexadienoic acid, wherein hydrogen on a methyl group at the ortho position of a carbonyl group in o-hydroxyacetophenone has higher activity and can perform addition reaction with the 2, 4-hexadienoic acid, so that an olefin group and a carboxyl group are introduced into the prepared grafting modifier, and because the ortho position of the phenolic hydroxyl group contains the carbonyl group, an intramolecular hydrogen bond is formed between the phenolic hydroxyl group and the carbonyl group to form a six-membered ring structure which is closed in a normal state, and the hydrogen bond is broken to release energy after ultraviolet irradiation, so that light energy is converted into heat energy, ultraviolet absorption is realized, and the anti-aging performance is realized;
and 4, step 4: adding the branched unsaturated polyester resin into an ethanol solution, stirring for dissolving, then adding azodiisobutyronitrile, heating to 70-80 ℃, then adding the grafting modifier, stirring for reacting for 1-2h, heating to 110-115 ℃, carrying out reflux reaction for 5-6h, then filtering, washing and drying to obtain the high-toughness polyester resin; wherein, 0.11 to 0.12g of azodiisobutyronitrile and 0.48 to 0.51g of grafting modifier are added into each gram of branched unsaturated polyester resin; because the branched unsaturated polyester resin contains unsaturated bonds, the branched unsaturated polyester resin can be polymerized with the grafting modifier under the initiation of azodiisobutyronitrile, and the grafting modifier is introduced into the prepared polyester resin, so that the polyester resin has certain ultraviolet absorption capacity and can resist aging.
The specific preparation process of the glass fiber reinforced material is as follows: adding glass fiber powder into acetone, stirring and mixing to prepare suspension, then adding (3-epoxypropylpropoxy) trimethoxy silane into the suspension, heating to 80-90 ℃, stirring and refluxing for reaction for 3-4h, and then filtering, washing and drying to obtain a glass fiber reinforced material; wherein 0.16-0.18g of (3-epoxypropylpropoxy) trimethoxy silane is added into each gram of glass fiber powder; because the surface of the glass fiber contains hydroxyl, and the oxysilane bond in the (3-epoxypropylpropoxy) trimethoxy silane can be subjected to alcoholysis to generate a-Si-OH bond, the-Si-OH can be reacted with the hydroxyl on the surface of the glass fiber to generate a-Si-O-bond, so that the (3-epoxypropylpropoxy) trimethoxy silane is grafted on the surface of the glass fiber, and a large amount of epoxy groups are introduced into the surface of the glass fiber;
the invention has the beneficial effects that:
1. according to the invention, the branched unsaturated polyester resin is prepared, and then the molecular chain of the branched unsaturated polyester resin is grafted with the modifier, so that a large number of phenolic hydroxyl groups are introduced into the prepared polyester resin, the ortho-position of the phenolic hydroxyl groups contains carbonyl groups, wherein intramolecular hydrogen bonds are formed between the phenolic hydroxyl groups and the carbonyl groups to form a six-membered ring structure, the ring structure is closed under a normal state, the hydrogen bonds are broken after ultraviolet irradiation to release energy, and then the energy is converted into heat energy to realize ultraviolet absorption, so that the anti-aging performance is realized, so that the polyester resin has higher anti-aging performance, the prepared polyester tile has a longer service life, and the problems that the toughness of the existing polyester resin is not high, the chemical medium resistance and the water resistance are poor, and meanwhile, the prepared resin tile is easy to age due to long-term ultraviolet irradiation, so that the performance of the resin tile is reduced, and the service life is short are solved.
2. The branched polyhydroxy modifier prepared by the invention has three hydroxyl groups at two ends, is connected through N atoms, the three groups connected by the N atoms are arranged in three different directions of a triangular cone, and the three hydroxyl groups at the two ends are crosslinked with maleic anhydride and react in three different directions to form a hyperbranched structure, so that the solubility of the branched unsaturated polyester resin is improved, and each crosslinked monomer branched polyhydroxy modifier contains long-chain flexible ether bonds, and the polymerized dendritic structure chain is formed by alternately connecting long-chain flexible ether bonds and unsaturated double bond structures, so that the toughness and the compatibility of the branched unsaturated polyester resin are greatly improved, the compatibility between the polyester resin and cloth and a glass fiber reinforced material can be greatly enhanced, and meanwhile, the high-toughness polyester resin contains a large amount of carboxyl groups which can react with epoxy groups in the glass fiber reinforced material, so that the glass fiber reinforced material is grafted on the high-toughness polyester resin chain, the prepared material has uniform and stable performance, and the problems of poor toughness and poor compatibility with an inorganic reinforced material of the existing polyester resin are solved.
3. According to the invention, the surfaces of the cotton cloth and the glass fiber reinforced material both contain the oxysilane bond, so that the prepared polyester tile has high hydrophobicity, and the phenomenon that the polyester tile absorbs water, is impregnated and corroded or causes water leakage of the polyester tile is effectively prevented.
4. According to the invention, the polyester resin and the reinforcing material are foamed through a foaming technology to prepare the polyester tile with a large number of foam holes, the prepared polyester tile has no reduction in strength, and the heat-insulating property of the polyester tile is improved due to the large number of foam holes, so that a higher heat-insulating effect is realized, and the problem of lower heat-insulating property of the polyester tile directly prepared from the polyester resin is solved.
Detailed Description
Example 1:
the specific preparation process of the high-toughness polyester resin comprises the following steps:
step 1: diethanolamine and ethylene glycol diglycidyl ether are mixed according to the mass ratio of 1:1, then adding water into the reaction vessel, uniformly stirring and mixing, heating to 60 ℃, stirring and reacting for 3 hours, and then carrying out reduced pressure distillation to obtain a branched polyhydroxy modifier, wherein the reaction structural formula is as follows;
step 2: weighing 100g of branched polyhydroxy modifier, adding into 1L of water, heating to 240-250 ℃, adding 8g of toluenesulfonic acid, stirring for 10min, adding 21g of maleic anhydride, carrying out constant-temperature reflux reaction for 10-12h, and then evaporating to obtain branched unsaturated polyester resin;
and step 3: 112g of 2, 4-hexadienoic acid and 8.7g of sodium ethoxide are added into 1L of acetone and stirred for dissolution, 136g of o-hydroxyacetophenone is added into the acetone, the mixture is stirred and mixed for reaction for 4 to 5 hours at normal temperature, then the solvent is removed by evaporation, and the product is added into water for recrystallization to obtain the grafting modifier, wherein the reaction structural formula is shown as follows;
and 4, step 4: adding 100g of branched unsaturated polyester resin into 1L of ethanol solution, stirring for dissolving, then adding 11g of azobisisobutyronitrile, heating to 70-80 ℃, then adding 48g of grafting modifier, stirring for reacting for 1-2h, heating to 110-115 ℃, carrying out reflux reaction for 5-6h, then filtering, washing and drying to obtain the high-toughness polyester resin.
Example 2:
the specific preparation process of the high-toughness polyester resin comprises the following steps:
step 1: diethanolamine and ethylene glycol diglycidyl ether are mixed according to the mass ratio of 1:1, then adding water into the reaction vessel, stirring and mixing the mixture uniformly, heating the mixture to 60 ℃, stirring and reacting the mixture for 3 hours, and then carrying out reduced pressure distillation to obtain a branched polyhydroxy modifier, wherein the reaction structural formula is as follows;
step 2: weighing 100g of branched polyhydroxy modifier, adding into 1L of water, heating to 240-250 ℃, adding 8g of toluenesulfonic acid, stirring for 10min, adding 21g of maleic anhydride, carrying out constant temperature reflux reaction for 10-12h, and then evaporating to obtain branched unsaturated polyester resin;
and step 3: adding 100g of branched unsaturated polyester resin into 1L of ethanol solution, stirring for dissolving, then adding 11g of azobisisobutyronitrile, heating to 70-80 ℃, then adding 48g of grafting modifier, stirring for reacting for 1-2h, heating to 110-115 ℃, carrying out reflux reaction for 5-6h, then filtering, washing and drying to obtain the high-toughness polyester resin.
Example 3:
the specific preparation process of the high-toughness polyester resin comprises the following steps:
step 1: weighing 100g of water, adding 1L of water, heating to 240-250 ℃, adding 8g of toluenesulfonic acid, stirring to react for 10min, adding 48g of maleic anhydride, carrying out constant-temperature reflux reaction for 10-12h, and then evaporating to obtain unsaturated polyester resin;
and 2, step: adding 112g of 2, 4-hexadienoic acid and 8.7g of sodium ethoxide into 1L of acetone, stirring for dissolving, then adding 136g of o-hydroxyacetophenone, stirring for mixing reaction for 4-5h at normal temperature, then evaporating to remove the solvent, adding the product into water, and recrystallizing to obtain the grafting modifier, wherein the reaction structural formula is shown as follows;
and 3, step 3: adding 100g of unsaturated polyester resin into 1L of ethanol solution, stirring for dissolving, then adding 11g of azobisisobutyronitrile, heating to 70-80 ℃, then adding 48g of grafting modifier, stirring for reacting for 1-2h, heating to 110-115 ℃, carrying out reflux reaction for 5-6h, then filtering, washing and drying to obtain the high-toughness polyester resin.
Example 4:
the specific preparation process of the glass fiber reinforced material is as follows: adding 100g of glass fiber powder into 80mL of acetone, stirring and mixing to prepare a suspension, then adding 16g of (3-epoxypropylpropoxy) trimethoxy silane into the suspension, heating to 80-90 ℃, stirring, refluxing and reacting for 3-4h, and then filtering, washing and drying to obtain the glass fiber reinforced material.
Example 5:
an environment-friendly polyester tile production process based on rag comprises the following specific process steps:
firstly, crushing 1kg of cotton cloth, adding the crushed cotton cloth into a stirring kettle, adding 2.3L of 35% sodium hydroxide solution, cooking for 4-5 hours at 70-80 ℃, filtering, washing and drying to obtain pretreated cotton cloth;
secondly, weighing 1.1mol of ammonia water and 1.1mol of epichlorohydrin, simultaneously adding the ammonia water and the epichlorohydrin into a reaction container, heating to 50 ℃, stirring and reacting for 5-6h, then adding 100g of pretreated cotton cloth and 0.6g of sodium hydroxide, heating to 100-110 ℃, performing reflux reaction for 13-14h, filtering, washing and drying to obtain aminated cotton cloth;
thirdly, adding 100g of aminated cotton cloth into 800mL of ethanol, uniformly stirring, adding (3-epoxypropylpropoxy) trimethoxy silane into 12g of aminated cotton cloth, heating to 40-50 ℃, and reacting for 6-7 hours with stirring to obtain hydrophobic cotton cloth;
fourthly, 98g of the high-toughness polyester resin prepared in the embodiment 1 is added into 400g of ethanol and stirred to be dissolved to form a glue solution, then 100g of hydrophobic cotton cloth, 20g of the glass fiber reinforced material prepared in the embodiment 4, 2.4g of the foaming agent, 3.9g of the release agent and 1.8g of toluene diisocyanate are added into the glue solution and stirred and mixed for 8 to 10 minutes, then the obtained mixed glue solution is poured into a mould and foamed and solidified for 30 minutes at the temperature of 170 ℃, and the environment-friendly polyester tile is obtained after the mixed glue solution is cooled and demoulded; wherein the foaming agent is sodium bicarbonate and foaming agent AC according to the mass ratio of 1:1 in the ratio of 1.
Example 6:
the specific technological process of the production process of the environment-friendly polyester tile based on the rag is the same as that of the example 5, and the high-toughness polyester resin prepared in the example 1 and used in the example 5 is replaced by the high-toughness polyester resin prepared in the example 2.
Example 7:
the process for producing the environment-friendly polyester tile based on the rag is the same as that in example 5, and the high-toughness polyester resin prepared in example 1 and used in example 5 is replaced by the high-toughness polyester resin prepared in example 3.
Example 8:
the production process of the environment-friendly polyester tile based on the rag is the same as that in the embodiment 5, and the glass fiber reinforced material prepared in the embodiment 4 used in the embodiment 5 is replaced by glass fiber.
Example 9:
the environment-friendly polyester tiles prepared in the examples 5 to 8 were put into a xenon lamp aging test chamber for aging treatment for 100 days, and the ultraviolet irradiation intensity was controlled to be 50mW/cm 2 The temperature is 60 ℃, the air humidity is 40%, then the flexural strength of the sample before and after aging is tested, and the measurement results are shown in table 1;
TABLE 1 flexural Strength of eco-friendly polyester tiles prepared in examples 5 to 8 before and after aging
As can be seen from table 1, the polyester tiles prepared in examples 5 and 6 have high flexural strength, and the glass fiber reinforced material is added, so that the high-toughness polyester resin is of a dendritic hyperbranched structure, and the medium-pretreated cotton cloth and the glass fiber reinforced material can be uniformly mixed after being added, and meanwhile, the high-toughness polyester resin contains a large amount of carboxyl groups, and can react with epoxy groups in the glass fiber reinforced material, so that the glass fiber reinforced material is grafted on a high-toughness polyester resin chain, so that the prepared material has uniform and stable performance, and because the grafting modifier is introduced in example 5, olefin groups and carboxyl groups are introduced in the grafting modifier, and because the ortho-position of the phenol hydroxyl group contains carbonyl groups, an intramolecular hydrogen bond is formed between the phenol hydroxyl group and the carbonyl groups, so that a six-membered ring structure is formed, the ring structure is closed in a normal state, and after ultraviolet irradiation, the hydrogen bond is broken to release energy, so that light energy is converted into heat energy, so that ultraviolet absorption is realized, and further, the anti-aging performance is realized, and the performance of the material is not affected under the effect of ultraviolet rays, and in example 6, because the grafting modifier is not introduced in the material, so that the polyester resin in the material is aged under the effect of ultraviolet rays, the long-term, the strength of the polyester resin is reduced; the polyester resin used in the preparation process of the polyester tile in the embodiment 7 is directly prepared by polymerization of the glycerol ether and the maleic anhydride, and the prepared product is of a straight-chain structure, so that the dispersion performance of the pretreated cotton cloth and the glass fiber reinforced material in the resin is reduced, the glass fiber reinforced material is unevenly dispersed, and the strength of the prepared polyester tile is reduced; the polyester tile prepared in the example 8 is directly added with the glass fiber, and the compatibility between the glass fiber and the organic resin is poor, so that the dispersion is easy to be uneven, and the performance of the polyester tile is further influenced.
The thermal conductivity of the polyester tiles prepared in examples 5 to 8 was measured, wherein the thermal conductivity of the polyester tile prepared in example 5 was 0.086W/(m.k), the thermal conductivity of the polyester tile prepared in example 6 was 0.085W/(m.k), the thermal conductivity of the polyester tile prepared in example 7 was 0.092W/(m.k), and the thermal conductivity of the polyester tile prepared in example 8 was 0.096W/(m.k), so that the polyester tile prepared in example 8 was a porous material of foamed material, and the added glass fiber had a certain thermal insulation property, thereby providing the polyester tile with high thermal insulation property, the thermal conductivity of which was 0.086W/(m.k), while the thermal insulation property of the polyester tiles prepared in examples 7 and 8 was reduced due to the uneven dispersion of the glass fiber.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (5)
1. The production process of the environment-friendly polyester tile based on the rag is characterized by comprising the following specific process steps of:
firstly, crushing cotton cloth, adding the crushed cotton cloth into a stirring kettle, adding a 35% sodium hydroxide solution into the stirring kettle, cooking the mixture for 4 to 5 hours at the temperature of between 70 and 80 ℃, and then filtering, washing and drying the mixture to obtain pretreated cotton cloth;
secondly, weighing a certain amount of ammonia water and epoxy chloropropane, simultaneously adding the ammonia water and the epoxy chloropropane into a reaction container, heating to 50-60 ℃, stirring for reaction for 5-6h, then adding pretreated cotton cloth and sodium hydroxide into the reaction container, heating to 100-110 ℃, performing reflux reaction for 13-14h, filtering, washing and drying to obtain aminated cotton cloth;
thirdly, adding the aminated cotton cloth into ethanol, uniformly stirring, adding (3-epoxypropyloxy) trimethoxy silane, heating to 40-50 ℃, stirring and reacting for 6-7 hours to obtain hydrophobic cotton cloth;
fourthly, adding the high-toughness polyester resin into ethanol, stirring and dissolving to form glue solution, then adding hydrophobic cotton cloth, glass fiber reinforced materials, foaming agents, release agents and curing agents into the glue solution, stirring and mixing for 8-10min, then pouring the obtained mixed glue solution into a mold, foaming and curing for 30min at 170 ℃, cooling and demolding to obtain the environment-friendly polyester tile;
in the second step, the ratio of ammonia to epichlorohydrin is 1:1, simultaneously adding 0.11-0.12mol of epichlorohydrin and 0.06g of sodium hydroxide into every 10 g of pretreated cotton cloth;
in the third step, 0.12-0.13g of (3-epoxypropylpropoxy) trimethoxy silane is added into each gram of aminated cotton cloth;
in the fourth step, hydrophobic cotton cloth, high-toughness polyester resin, glass fiber reinforced materials, foaming agents, release agents and curing agents are mixed according to the mass ratio of 100:96-107:19-23:2.4-2.5:3.9-4.2:1.8-1.9, wherein the foaming agent is sodium bicarbonate and foaming agent AC according to the mass ratio of 1:1, and the curing agent is one or more of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate;
the specific preparation process of the high-toughness polyester resin is as follows:
step 1: adding diethanol amine into water, stirring and mixing uniformly, then adding ethylene glycol diglycidyl ether into the mixture, heating to 60-70 ℃, stirring and reacting for 2-3 hours, and then carrying out reduced pressure distillation to obtain a branched polyhydroxy modifier, wherein the reaction structural formula is as follows;
and 2, step: weighing a certain amount of branched polyhydroxy modifier, adding into water, heating to 240-250 ℃, adding p-toluenesulfonic acid, stirring for reaction for 10min, adding maleic anhydride, carrying out constant-temperature reflux reaction for 10-12h, and then evaporating to obtain branched unsaturated polyester resin;
and step 3: adding 2, 4-hexadienoic acid and sodium ethoxide into acetone, stirring and dissolving, then adding o-hydroxyacetophenone into the acetone, stirring and mixing the mixture at normal temperature for reaction for 4 to 5 hours, then evaporating the mixture to remove the solvent, and adding the product into water for recrystallization to obtain a grafting modifier, wherein the reaction structural formula is shown as follows;
and 4, step 4: adding the branched unsaturated polyester resin into an ethanol solution, stirring for dissolving, then adding azodiisobutyronitrile, heating to 70-80 ℃, then adding the grafting modifier, stirring for reacting for 1-2h, heating to 110-115 ℃, carrying out reflux reaction for 5-6h, then filtering, washing and drying to obtain the high-toughness polyester resin;
in the step 4, 0.11-0.12g of azobisisobutyronitrile and 0.48-0.51g of grafting modifier are added into each gram of branched unsaturated polyester resin.
2. The process for producing environment-friendly polyester tiles based on rags according to claim 1, wherein 0.21 to 0.23g of maleic anhydride and 0.08g of p-toluenesulfonic acid are added to each gram of branched polyhydroxy modifier in step 2.
3. The production process of the rag-based environment-friendly polyester tile according to claim 1, wherein in step 3, the ratio of the 2, 4-hexadienoic acid to the o-hydroxyacetophenone is 1:1, and adding 8.7-9.2g of sodium ethoxide into each mole of 2, 4-hexadienoic acid.
4. The production process of the environment-friendly polyester tile based on broken cloth according to claim 1, characterized in that the specific preparation process of the glass fiber reinforced material is as follows: adding glass fiber powder into acetone, stirring and mixing to prepare suspension, then adding (3-epoxypropyloxy) trimethoxy silane into the suspension, heating to 80-90 ℃, stirring, refluxing and reacting for 3-4h, and then filtering, washing and drying to obtain the glass fiber reinforced material.
5. The process for producing environment-friendly polyester tiles based on rags, according to claim 4, wherein (3-glycidoxypropyl) trimethoxysilane is added in an amount of 0.16-0.18g per gram of the glass fiber powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911274266.4A CN110951202B (en) | 2019-12-12 | 2019-12-12 | Production process of environment-friendly polyester tile based on rag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911274266.4A CN110951202B (en) | 2019-12-12 | 2019-12-12 | Production process of environment-friendly polyester tile based on rag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110951202A CN110951202A (en) | 2020-04-03 |
| CN110951202B true CN110951202B (en) | 2022-11-08 |
Family
ID=69981249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911274266.4A Active CN110951202B (en) | 2019-12-12 | 2019-12-12 | Production process of environment-friendly polyester tile based on rag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110951202B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227230A (en) * | 1998-12-28 | 1999-09-01 | 江苏省化工研究所 | Synthesis of foamed thermoplastic hard polyurethane plastic |
| CN101454132A (en) * | 2006-05-25 | 2009-06-10 | 三菱工程塑料株式会社 | Moldings of fiber-reinforced thermoplastic resin |
| CN103930461A (en) * | 2011-12-27 | 2014-07-16 | 东丽株式会社 | Epoxy resin composition for fiber-reinforced composite materials, prepreg, and fiber-reinforced composite material |
| CN106280517A (en) * | 2016-08-10 | 2017-01-04 | 南宁市邦得力木业有限责任公司 | A kind of environment-protection ground plate substrate |
-
2019
- 2019-12-12 CN CN201911274266.4A patent/CN110951202B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227230A (en) * | 1998-12-28 | 1999-09-01 | 江苏省化工研究所 | Synthesis of foamed thermoplastic hard polyurethane plastic |
| CN101454132A (en) * | 2006-05-25 | 2009-06-10 | 三菱工程塑料株式会社 | Moldings of fiber-reinforced thermoplastic resin |
| CN103930461A (en) * | 2011-12-27 | 2014-07-16 | 东丽株式会社 | Epoxy resin composition for fiber-reinforced composite materials, prepreg, and fiber-reinforced composite material |
| CN106280517A (en) * | 2016-08-10 | 2017-01-04 | 南宁市邦得力木业有限责任公司 | A kind of environment-protection ground plate substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110951202A (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qi et al. | Epoxidized soybean oil cured with tannic acid for fully bio-based epoxy resin | |
| CN101328243B (en) | Polypropylene acid imide foam material and preparation thereof | |
| CN101735405B (en) | Imitation marble unsaturated polyester resin and preparation method thereof | |
| Chiou et al. | Incorporation of natural renewable components and waste byproducts to benzoxazine based high performance materials | |
| CN104693150A (en) | Flexible epoxy resin and preparation method thereof | |
| CN112831041B (en) | Terephthalic acid type unsaturated polyester and preparation method thereof | |
| JP2014520936A (en) | Composition for producing tannin-based foam material, foam material obtainable therefrom, and method for producing the same | |
| Wu et al. | Synthesis and characterization of biobased polyurethane/SiO 2 nanocomposites from natural Sapium sebiferum oil | |
| CN107216608B (en) | A kind of compositions of thermosetting resin of highly corrosion resistant and its application | |
| CN108084402A (en) | A kind of hemicellulose base epoxy and preparation method thereof | |
| CN111139021B (en) | Low-temperature-curable high-adhesion heat-resistant cyanate ester adhesive and preparation method thereof | |
| CN114426767B (en) | Sheet molding compound and preparation method thereof | |
| CN111334001A (en) | High-thermal-conductivity boron nitride modified epoxy resin insulating material and preparation method thereof | |
| CN110951202B (en) | Production process of environment-friendly polyester tile based on rag | |
| CN114316515A (en) | Modified epoxy grouting material with ultra-long service life and preparation method thereof | |
| CN109679242A (en) | A kind of foaming shock resistance insulating board for building and preparation method thereof | |
| CN111748083B (en) | High-toughness polyester resin and synthesis method thereof | |
| CN115975526A (en) | Low-moisture-absorption epoxy adhesive film and preparation method thereof | |
| Russell et al. | Examining the influence of carboxylic anhydride structures on the reaction kinetics and processing characteristics of an epoxy resin for wind turbine applications | |
| JPH11116566A (en) | Cyclic carbonate resin composition and its cured product | |
| CN108084930A (en) | A kind of LED display binding agent and preparation method thereof | |
| CN105419704B (en) | A kind of urea-formaldehyde resin adhesive and preparation method thereof | |
| CN111073579B (en) | High-initial-viscosity polyurethane adhesive for artificial board and preparation method and application thereof | |
| CN109233710B (en) | Insulating material with high glass transition temperature and high-temperature cohesiveness and preparation method thereof | |
| JP2014136741A (en) | Resin composition and resin molding |
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 |