CN112062924B - Polyurethane resin for winding process, resin/fiber composite material, and preparation method and application thereof - Google Patents
Polyurethane resin for winding process, resin/fiber composite material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN112062924B CN112062924B CN202010852107.4A CN202010852107A CN112062924B CN 112062924 B CN112062924 B CN 112062924B CN 202010852107 A CN202010852107 A CN 202010852107A CN 112062924 B CN112062924 B CN 112062924B
- Authority
- CN
- China
- Prior art keywords
- resin
- composite material
- fiber composite
- preparing
- epoxy
- 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
- 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
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7607—Compounds of C08G18/7614 and of C08G18/7657
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- 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
- C08K7/06—Elements
-
- 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
- C08K7/10—Silicon-containing compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane resin and a resin/fiber composite material for a winding process, and preparation methods and applications thereof, and belongs to the field of resin synthesis and composite material preparation. The method comprises the following steps: (1) preparing an epoxy-terminated urethane mixture; (2) preparing a curing agent component; (3) mixing resin and a curing agent according to a certain proportion to prepare a sizing material, and placing the sizing material in a resin glue groove of winding equipment; (4) adopting winding equipment with an internal curing function, enabling continuous fibers to be fully mixed with resin through a glue groove, winding the mixture onto a mold according to a pre-designed direction and angle, opening a mold temperature controller connected with a mold core rod to heat the mold to a specified temperature, and finishing post-curing of a product; (5) and (6) demolding. The resin sizing material obtained by the invention has the advantages of long operable time, good mechanical property, no need of additionally building a heating channel and strong flexibility of the prepared composite material tower.
Description
Technical Field
The invention belongs to the field of resin synthesis and composite material preparation, and particularly relates to a polyurethane resin and a resin/fiber composite material for a winding process, and a preparation method and application thereof.
Background
The winding process is that the continuous fiber (or cloth belt, presoaked yarn) soaked in resin glue solution is wound on the core mould according to a certain rule, and then the product is obtained after solidification and demoulding. Most of the resins suitable for the winding process are epoxy resin, phenolic resin, vinyl resin, unsaturated resin and the like, for example, patent CN105219046A of Jiangsu Hengshen company. On the one hand, the above resins have basically environmental problems such as formaldehyde in phenol resins, styrene in vinyl resins and unsaturated resins; on the other hand, the composite material prepared by the resin has large brittleness and small deflection, and is not suitable for large-scale towers such as power grid poles and communication signal towers. In order to solve the above problems, basf corporation introduced a polyurethane type winding resin having more excellent environmental protection and flexibility, and dow corporation also disclosed a preparation method of the polyurethane winding resin in patent CN 108368279A. The technologies mainly adopt conventional two-component polyurethane resin, have operability time of about 30-40min at 25 ℃ and have positive effect on producing small-sized pipelines or towers.
The large winding pipeline and tower require that the resin operation time is at least more than 60min, but the two-component polyurethane resin can not meet the requirement, so that a new resin which can solve the problems of environmental protection and mechanical property defects of epoxy, phenolic aldehyde, vinyl, unsaturated resin and the like and the problem of short operation time of the polyurethane resin is needed to be developed.
Disclosure of Invention
The purpose of the invention is as follows: provides a polyurethane resin for a winding process, a resin/fiber composite material, a preparation method and application thereof, which aim to solve the problems involved in the background technology.
The technical scheme is as follows: the invention provides a preparation method of polyurethane resin for a winding process, which comprises the following steps: heating binary epoxy resin to 100-120 ℃, vacuumizing to remove water for 0.5-2 hours, adding a small molecular monocarboxyl compound and a certain amount of catalyst according to the molar ratio of epoxy group to carboxyl group of (1.5-2.4): 1 at the temperature of 80-140 ℃, reacting for 0.5-4 hours to obtain a compound simultaneously containing hydroxyl and epoxy group, adding an isocyanate compound at normal temperature according to the molar ratio of isocyanate group to hydroxyl group of 1 (0.8-1.5), and continuously reacting for 6-10 hours to obtain an epoxy group-terminated carbamate mixture.
As a preferable scheme, the binary epoxy resin is one or a mixture of more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether and hexanediol diglycidyl ether; the small molecular single carboxyl compound is one of acetic acid, propionic acid, butyric acid and valeric acid.
As a preferable scheme, the catalyst is one of p-toluenesulfonic acid, triphenylphosphine and triethylamine;
as a preferable mode, the amount of the catalyst is 0.1 to 1% by weight based on the total weight of the reaction system.
As a preferable scheme, the isocyanate is one or more of polymeric diphenylmethane diisocyanate (polymeric MDI), 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate, Toluene Diisocyanate (TDI), isophorone diisocyanate, Hexamethylene Diisocyanate (HDI) and hydrogenated diphenylmethane diisocyanate (HMDI).
The invention also provides polyurethane resin for the winding process, and the epoxy-terminated urethane mixture is obtained based on the preparation method of the polyurethane resin for the winding process.
The invention also provides a preparation method of the resin/fiber composite material, which comprises the following steps:
step one, preparation of an epoxy-terminated urethane mixture:
heating binary epoxy resin to 100-120 ℃, vacuumizing to remove water for 0.5-2 hours, adding a small molecular monocarboxyl compound and a certain amount of catalyst according to the molar ratio of epoxy group to carboxyl group of (1.5-2.4): 1 at the temperature of 80-140 ℃, reacting for 0.5-4 hours to obtain a compound simultaneously containing hydroxyl and epoxy group, adding an isocyanate compound at normal temperature according to the molar ratio of isocyanate group to hydroxyl group of 1 (0.8-1.5), and continuously reacting for 6-10 hours to obtain an epoxy group-terminated carbamate mixture.
Step two, preparation of curing agent components:
the curing agent comprises the following components in percentage by weight:
10-30% of high molecular weight amino-terminated polyether,
30-60% of low molecular weight amino-terminated polyether,
10 to 20 percent of small molecular ammonia curing agent,
1 to 2 percent of water removing agent,
1-2% of defoaming agent.
Step three, mixing:
mixing the carbamate mixture and the curing agent component according to the molar ratio of epoxy groups to amino groups (1.5-1): 1, and placing the mixture into a resin glue tank of winding equipment.
Step four, winding and curing:
and (3) winding equipment with an internal curing function is adopted, so that after the continuous fibers are fully mixed with the resin through the glue groove, the fiber content is 25% -40%, the continuous fibers are wound on the die according to a fixed direction and angle, and a die temperature machine connected with a die core rod is opened to heat the die to a specified temperature, so that the post-curing of the product is completed.
And step five, demolding.
As a preferable scheme, the binary epoxy resin is one or a mixture of more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether and hexanediol diglycidyl ether; the small molecular single carboxyl compound is one of acetic acid, propionic acid, butyric acid and valeric acid.
As a preferable scheme, the catalyst is one of p-toluenesulfonic acid, triphenylphosphine and triethylamine;
as a preferable mode, the amount of the catalyst is 0.1 to 1% by weight based on the total weight of the reaction system.
As a preferable scheme, the isocyanate is one or more of polymeric diphenylmethane diisocyanate (polymeric MDI), 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate, Toluene Diisocyanate (TDI), isophorone diisocyanate, Hexamethylene Diisocyanate (HDI) and hydrogenated diphenylmethane diisocyanate (HMDI).
As a preferred embodiment, the high molecular weight amino-terminated polyether and the low molecular weight amino-terminated polyether correspond to the following general formula,
wherein the n value of the high molecular weight amino-terminated polyether is 10-30, and the n value of the low molecular weight amino-terminated polyether is 1-6.
As a preferable scheme, the small molecular ammonia curing agent is one of isophorone diamine (IPDA) and diaminodicyclohexyl methane (HMDA).
Preferably, the water scavenger is one of oxazolidine, orthoformate and carbodiimide water scavengers.
Preferably, the defoaming agent is a fluorine defoaming agent.
As a preferred scheme, the continuous fiber is one or more of glass fiber, basalt fiber and carbon fiber.
As a preferable scheme, the heating temperature of the mold temperature controller is 50-80 ℃.
The invention also provides a resin/fiber composite material, and the glass fiber reinforced plastic material with excellent flexibility is obtained based on the preparation method of the resin/fiber composite material.
The invention also provides an application of the resin/fiber composite material in preparing large-scale pipelines and pole tower composite materials, serving as the large-scale pipelines and pole tower composite materials or serving as components of the large-scale pipelines and pole tower composite materials.
Has the advantages that: the invention relates to a polyurethane resin and resin/fiber composite material for winding process, and a preparation method and application thereof, compared with the prior art, the method of the invention has the following advantages: (1) compared with the traditional epoxy resin, the flexibility of the resin casting body and the composite material thereof is obviously improved and is equivalent to the well-known polyurethane resin with good flexibility; (2) compared with the traditional polyurethane resin, the resin provided by the invention has obviously prolonged operable time, is equivalent to the known epoxy resin, unsaturated resin and the like with long operating time, and has obvious advantages for producing large-scale pipelines or towers; (3) the cost is not obviously improved. The invention is modified on the basis of polyurethane resin raw materials, and finally cured by adopting an epoxy group curing mode. The polyurethane resin in China has huge raw material productivity and cheap raw materials, and the price of the modified carbamate epoxy resin is even lower than that of the traditional epoxy resin.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents, instruments or equipment of any manufacturer not indicated are commercially available.
Example 1
Step 1: heating 1580g of ethylene glycol diglycidyl ether to 120 ℃, vacuumizing for dewatering for 1 hour, adding 600g of acetic acid and 16g of triphenylphosphine catalyst according to the molar ratio of epoxy group to carboxyl group of 2:1 at 80 ℃, reacting for 4 hours to obtain a compound containing both hydroxyl and epoxy groups, adding 1250g of a mixture of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate (any ratio) according to the molar ratio of isocyanate group to hydroxyl group of 1:1 at normal temperature, and continuously reacting for 6 hours to obtain an epoxy group-terminated carbamate mixture.
Step 2: the curing agent is prepared from the following components in percentage by weight:
30% of high molecular weight amino-terminated polyether and n =30
Low molecular weight amino terminated polyether 60%, n =1
IPDA 10%
Oxazolidine water scavenger (ALT-101, Hunan Anxiang Airit chemical Co., Ltd.) 1%
Fluorine-based antifoaming agent (MTK-4352, New materials of Nantong Martai Co., Ltd.) 1%.
And step 3: and (3) mixing the epoxy resin prepared in the step (1) and the curing agent component prepared in the step (2) according to the molar ratio of epoxy group to amino group of 1:1, and placing the mixture into a resin glue tank of winding equipment.
And 4, step 4: and (3) adopting winding equipment with an internal curing function, fully mixing the continuous basalt fibers with the resin through a glue groove, winding the continuous basalt fibers to the mold according to a fixed direction and angle, opening a mold temperature machine connected with a mold core rod, heating the mold to 80 ℃, and finishing post-curing of the product.
And 5: and (6) demolding.
Example 2
Step 1: heating 2020g of butanediol diglycidyl ether to 120 ℃, vacuumizing for removing water for 1 hour, adding 740g of propionic acid and 2.76g of p-toluenesulfonic acid catalyst according to the molar ratio of epoxy group to carboxyl group of 2:1 at 140 ℃, reacting for 0.5 hour to obtain a compound simultaneously containing hydroxyl group and epoxy group, adding 1335g of polymeric diphenylmethane diisocyanate (commonly known as black material) according to the molar ratio of isocyanate group to hydroxyl group of 1:1, and continuously reacting for 10 hours to obtain an epoxy group-terminated carbamate mixture.
Step 2: the curing agent is prepared from the following components in percentage by weight:
high molecular weight amino terminated polyether 10%, n =10
Low molecular weight amino terminated polyether 60%, n =6
IPDA 20%
Proformicacid triester dehydrator (Bailingwei Co.) 2%
2% of a fluorine-based antifoaming agent (MTK-4352, New Nantong Martai Co., Ltd.).
And 3, mixing the epoxy resin prepared in the step 1 and the curing agent component prepared in the step 2 according to the molar ratio of epoxy group to amino group of 1:1, and placing the mixture in a resin glue tank of winding equipment.
And 4, step 4: and (3) adopting winding equipment with an internal curing function, fully mixing the continuous glass fiber with the resin through a glue groove, winding the continuous glass fiber to the mold according to a fixed direction and angle, and opening a mold temperature machine connected with the mold core rod to heat the mold to 50 ℃ to finish post-curing of the product.
And 5: and (6) demolding.
Example 3
Step 1: heating 2300g of hexanediol diglycidyl ether to 120 ℃, vacuumizing and removing water for 1 hour, adding 880g of butyric acid and 15.9g of triethylamine catalyst according to the molar ratio of epoxy group to carboxyl group being 2:1 at 120 ℃, reacting for 2 hours to obtain a compound containing both hydroxyl group and epoxy group, adding 1104.5g of a mixture of polymeric diphenylmethane diisocyanate (667 g) and methylphenyl diisocyanate (437.5 g) according to the molar ratio of isocyanate group to hydroxyl group being 1:1 at normal temperature, and continuing to react for 8 hours to obtain an epoxy group-terminated urethane mixture.
Step 2: the curing agent is prepared from the following components in percentage by weight:
30% of high molecular weight amino-terminated polyether and n =20
20% of low molecular weight amino-terminated polyether and n =4
HMDA 20%
Carbodiimide water scavenger (DMAP, carbofuran) 2%
Fluorine defoaming agent (MTK-4352, New Nantong Martaike Material Co., Ltd.) 1.5%
And step 3: and (3) mixing the epoxy resin prepared in the step (1) and the curing agent component prepared in the step (2) according to the molar ratio of epoxy group to amino group of 1:1, and placing the mixture into a resin glue tank of winding equipment.
And 4, step 4: and (3) adopting winding equipment with an internal curing function, fully mixing the continuous glass fiber with the resin through a glue groove, winding the continuous glass fiber to the mold according to a fixed direction and angle, opening a mold temperature machine connected with the mold core rod, heating the mold to 70 ℃, and finishing post-curing of the product.
And 5: and (6) demolding.
Example 4
Step 1: heating 2300g of hexanediol diglycidyl ether to 120 ℃, vacuumizing and removing water for 1 hour, adding 1020g of butyric acid and 13.28g of triphenylphosphine catalyst according to the molar ratio of epoxy group to carboxyl group of 2:1 at 120 ℃, reacting for 3 hours to obtain a compound containing both hydroxyl and epoxy groups, adding 1110g of isophorone diisocyanate at normal temperature according to the molar ratio of isocyanate group to hydroxyl group of 1:1, and continuously reacting for 9 hours to obtain an epoxy group-blocked carbamate mixture.
Step 2: the curing agent is prepared from the following components in percentage by weight:
high molecular weight amino terminated polyether 20%, n =17
Low molecular weight amino terminated polyether 50%, n =2
HMDA 10%
Carbodiimide water scavenger (DMAP, carbofuran) 1%
Fluorine defoaming agent (MTK-4352, New Nantong Martaike Material Co., Ltd.) 1%
And step 3: and (3) mixing the epoxy resin prepared in the step (1) and the curing agent component prepared in the step (2) according to the molar ratio of epoxy group to amino group of 1:1, and placing the mixture into a resin glue tank of winding equipment.
And 4, step 4: and (3) winding equipment with an internal curing function is adopted, so that after the continuous carbon fibers are fully mixed with the resin through the glue groove, the fiber content is 25%, the continuous carbon fibers are wound on the die according to a fixed direction and angle, the die is heated to 60 ℃ by opening a die temperature machine connected with a die core rod, and the post-curing of the product is completed.
And 5: and (6) demolding.
Example 5
Step 1: 1844g of a mixture of ethylene glycol diglycidyl ether (632 g) and butanediol diglycidyl ether (1212 g) is heated to 120 ℃, vacuumized to remove water for 1 hour, 600g of acetic acid and 4.88g of triethylamine catalyst are added at 100 ℃ according to the molar ratio of epoxy group to carboxyl group of 2:1 to react for 2.5 hours to obtain a compound simultaneously containing hydroxyl and epoxy group, 840g of hexamethylene diisocyanate is added at normal temperature according to the molar ratio of isocyanate group to hydroxyl group of 1:1 to continue to react for 7 hours to obtain an epoxy group-terminated urethane mixture.
Step 2: the curing agent is prepared from the following components in percentage by weight:
high molecular weight amino terminated polyether 25%, n =23
40% of low molecular weight amino-terminated polyether and n =3
HMDA 15%
Oxazolidine water scavenger (ALT-101, Hunan Anxiang Airit chemical Co., Ltd.) 1.6%
Fluorine defoaming agent (MTK-4352, New Nantong Martaike Material Co., Ltd.) 1.8%
And step 3: and (3) mixing the epoxy resin prepared in the step (1) and the curing agent component prepared in the step (2) according to the molar ratio of epoxy group to amino group of 1:1, and placing the mixture into a resin glue tank of winding equipment.
And 4, step 4: and (3) adopting winding equipment with an internal curing function, fully mixing the continuous carbon fibers with the resin through a glue groove, winding the continuous carbon fibers to the mold according to a fixed direction and angle, opening a mold temperature machine connected with a mold core rod to heat the mold to 65 ℃, and finishing post-curing of the product.
And 5: and (6) demolding.
Example 6
Step 1: heating 1724g of a mixture of ethylene glycol diglycidyl ether (1264 g) and hexanediol diglycidyl ether (460 g) to 120 ℃, vacuumizing for removing water for 1 hour, adding 1020g of acetic acid and 16.26g of p-toluenesulfonic acid catalyst according to the molar ratio of epoxy groups to carboxyl groups being 2:1 at 90 ℃, reacting for 3.5 hours to obtain a compound simultaneously containing hydroxyl groups and epoxy groups, adding 1270g of hydrogenated diphenylmethane diisocyanate according to the molar ratio of isocyanate groups to hydroxyl groups being 1:1 at normal temperature, and continuously reacting for 7.5 hours to obtain an epoxy group-terminated carbamate mixture.
Step 2: the curing agent is prepared from the following components in percentage by weight:
28% of high molecular weight amino terminated polyether, n =13
52% of low molecular weight amino-terminated polyether, and n =5
IPDA 13%
Oxazolidine water scavenger (ALT-101, Hunan Anxiang Airit chemical Co., Ltd.) 1.2%
Fluorine-based antifoaming agent (MTK-4352, New materials of Nantong Martai Co., Ltd.) 1.3%.
And 3, mixing the epoxy resin prepared in the step 1 and the curing agent component prepared in the step 2 according to the molar ratio of epoxy group to amino group of 1:1, and placing the mixture in a resin glue tank of winding equipment.
And 4, step 4: and (2) adopting winding equipment with an internal curing function to ensure that the continuous glass fiber and the basalt fiber (the weight ratio is 8: 2) are fully mixed with the resin through a glue groove, the fiber content is 37 percent, the continuous glass fiber and the basalt fiber are wound on a die according to a fixed direction and angle, a die temperature machine connected with a die core rod is opened to heat the die to 75 ℃, and the post-curing of the product is completed.
And 5: and (6) demolding.
Example 7
Step 1: a mixture of 1724g ethylene glycol diglycidyl ether (1264 g) and hexanediol diglycidyl ether (460 g) was warmed to 100 ℃ and evacuated to remove water for 2 hours at 90 ℃ in a molar ratio of epoxy to carboxyl of 2.4: adding 1020g of acetic acid and 16.26g of p-toluenesulfonic acid catalyst according to the proportion of 1, reacting for 3.5 hours to obtain a compound simultaneously containing hydroxyl and epoxy, adding 1270g of hydrogenated diphenylmethane diisocyanate according to the molar ratio of isocyanate group to hydroxyl of 1:1.5, and continuing to react for 7.5 hours to obtain an epoxy-terminated carbamate mixture.
Step 2: the curing agent is prepared from the following components in percentage by weight:
28% of high molecular weight amino terminated polyether, n =13
52% of low molecular weight amino-terminated polyether, and n =5
IPDA 13%
Oxazolidine water scavenger (ALT-101, Hunan Anxiang Airit chemical Co., Ltd.) 1.2%
Fluorine-based antifoaming agent (MTK-4352, New materials of Nantong Martai Co., Ltd.) 1.3%.
And 3, mixing the epoxy resin prepared in the step 1 and the curing agent component prepared in the step 2 according to the molar ratio of epoxy group to amino group of 1:1, and placing the mixture in a resin glue tank of winding equipment.
And 4, step 4: and (2) adopting winding equipment with an internal curing function to ensure that the continuous glass fiber and the basalt fiber (the weight ratio is 8: 2) are fully mixed with the resin through a glue groove, the fiber content is 37 percent, the continuous glass fiber and the basalt fiber are wound on a die according to a fixed direction and angle, a die temperature machine connected with a die core rod is opened to heat the die to 75 ℃, and the post-curing of the product is completed.
And 5: and (6) demolding.
Example 8
Step 1: heating 1724g of a mixture of ethylene glycol diglycidyl ether (1264 g) and hexanediol diglycidyl ether (460 g) to 120 ℃, vacuumizing to remove water for 0.5 hour, adding 1020g of acetic acid and 16.26g of p-toluenesulfonic acid catalyst at 90 ℃ according to the molar ratio of epoxy groups to carboxyl groups being 1.5:1, reacting for 3.5 hours to obtain a compound simultaneously containing hydroxyl groups and epoxy groups, adding 1270g of hydrogenated diphenylmethane diisocyanate at normal temperature according to the molar ratio of isocyanate groups to hydroxyl groups being 1:0.8, and continuously reacting for 7.5 hours to obtain an epoxy group-terminated carbamate mixture.
Step 2: the curing agent is prepared from the following components in percentage by weight:
28% of high molecular weight amino terminated polyether, n =13
52% of low molecular weight amino-terminated polyether, and n =5
IPDA 13%
Oxazolidine water scavenger (ALT-101, Hunan Anxiang Airit chemical Co., Ltd.) 1.2%
Fluorine-based antifoaming agent (MTK-4352, New materials of Nantong Martai Co., Ltd.) 1.3%.
And 3, mixing the epoxy resin prepared in the step 1 and the curing agent component prepared in the step 2 according to the molar ratio of epoxy group to amino group of 1:1, and placing the mixture in a resin glue tank of winding equipment.
And 4, step 4: and (2) adopting winding equipment with an internal curing function to ensure that the continuous glass fiber and the basalt fiber (the weight ratio is 8: 2) are fully mixed with the resin through a glue groove, the fiber content is 37 percent, the continuous glass fiber and the basalt fiber are wound on a die according to a fixed direction and angle, a die temperature machine connected with a die core rod is opened to heat the die to 75 ℃, and the post-curing of the product is completed.
And 5: and (6) demolding.
Comparative examples 1 to 6
The fiber reinforced resin composite material product is prepared by respectively adopting the processes of the same fiber winding direction and angle, the same fiber type and content and the same corresponding embodiment for performance test, wherein the resin is: epoxy resin (comparative example 1), unsaturated resin (comparative example 2), vinyl resin (comparative example 3), phenol resin (comparative example 4), urethane-modified unsaturated resin (comparative example 5), and urethane-modified epoxy resin (comparative example 6)
Note: the test sample is a conical tower test method with the length of 18m, the diameter of the upper edge of 190mm and the diameter of the bottom of 300 mm: the bottom is fixed and the load is applied to the top until the tower is damaged.
From the test data in the table, it can be seen that the composite material tower prepared by the resin has obvious advantages in resisting load damage compared with the traditional resin under the condition that the types, the quantity, the content, the winding angles and the directions of the fibers are the same.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (13)
1. A preparation method of a resin/fiber composite material is characterized by comprising the following steps:
step one, preparation of an epoxy-terminated urethane mixture:
heating binary epoxy resin to 100-120 ℃, vacuumizing to remove water for 0.5-2 hours, adding a small molecular monocarboxyl compound and a certain amount of catalyst according to the molar ratio of epoxy group to carboxyl group of (1.5-2.4): 1 at the temperature of 80-140 ℃, reacting for 0.5-4 hours to obtain a compound simultaneously containing hydroxyl and epoxy group, adding an isocyanate compound at normal temperature according to the molar ratio of isocyanate group to hydroxyl group of 1 (0.8-1.5), and continuously reacting for 6-10 hours to obtain an epoxy group-terminated carbamate mixture;
step two, preparation of curing agent components:
the curing agent comprises the following components in percentage by weight:
10-30% of high molecular weight amino-terminated polyether,
30-60% of low molecular weight amino-terminated polyether,
10 to 20 percent of small molecular ammonia curing agent,
1 to 2 percent of water removing agent,
1-2% of defoaming agent;
the sum of all the components in the curing agent component is 100 percent;
wherein the high molecular weight amino terminated polyether and the low molecular weight amino terminated polyether are in accordance with the following general formulas,
wherein the n value of the high molecular weight amino-terminated polyether is 10-30, and the n value of the low molecular weight amino-terminated polyether is 1-6;
step three, mixing:
mixing the carbamate mixture and the curing agent component according to the molar ratio of epoxy groups to amino groups (1.5-1): 1, and placing the mixture in a resin glue tank of winding equipment;
step four, winding and curing:
adopting winding equipment with an internal curing function, enabling the continuous fibers to pass through a glue groove to be fully mixed with resin, enabling the content of the fibers to be 25% -40%, winding the fibers onto a mold according to a fixed direction and angle, opening a mold temperature machine connected with a mold core rod to heat the mold to a specified temperature, and completing post-curing of a product;
and step five, demolding.
2. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the binary epoxy resin is one or a mixture of more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether and hexanediol diglycidyl ether.
3. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the small molecular single carboxyl compound is one of acetic acid, propionic acid, butyric acid and valeric acid.
4. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the catalyst is one of p-toluenesulfonic acid, triphenylphosphine and triethylamine.
5. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the amount of the catalyst is 0.1-1% of the total weight of the reaction system.
6. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the isocyanate is one or more of polymeric diphenylmethane diisocyanate, 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.
7. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the micromolecular ammonia curing agent is one of isophorone diamine and diaminodicyclohexyl methane.
8. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the water remover is one of oxazolidine, orthoformate and carbodiimide water removers.
9. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the defoaming agent is a fluorine defoaming agent.
10. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the continuous fiber is one or more of glass fiber, basalt fiber and carbon fiber.
11. The method for preparing a resin/fiber composite material according to claim 1, characterized in that: the heating temperature of the mold temperature controller is 50-80 ℃.
12. A resin/fiber composite material, which is made of a glass fiber reinforced plastic material with excellent flexibility based on the preparation method of the resin/fiber composite material as claimed in any one of claims 1 to 11.
13. Use of the resin/fibre composite according to claim 12 for the production of large pipes and towers, as well as for large pipes and towers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010852107.4A CN112062924B (en) | 2020-08-21 | 2020-08-21 | Polyurethane resin for winding process, resin/fiber composite material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010852107.4A CN112062924B (en) | 2020-08-21 | 2020-08-21 | Polyurethane resin for winding process, resin/fiber composite material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112062924A CN112062924A (en) | 2020-12-11 |
| CN112062924B true CN112062924B (en) | 2022-04-01 |
Family
ID=73659931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010852107.4A Active CN112062924B (en) | 2020-08-21 | 2020-08-21 | Polyurethane resin for winding process, resin/fiber composite material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112062924B (en) |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0689290B2 (en) * | 1989-09-27 | 1994-11-09 | 大日本塗料株式会社 | Paint composition |
| CN1093377A (en) * | 1994-01-11 | 1994-10-12 | 青岛化工学院 | The preparation method of the urethane-epoxy resin composite material of high strength, high tenacity and high-wearing feature |
| US5480958A (en) * | 1994-09-21 | 1996-01-02 | Air Products And Chemicals, Inc. | Polyepoxide resins incorporating epoxy terminated urethanes as tougheners |
| JP2000053843A (en) * | 1998-08-12 | 2000-02-22 | Toto Kogyo Kk | Epoxy resin composition for molding material and electric /electronic parts |
| JP2001100410A (en) * | 1999-09-29 | 2001-04-13 | Nippon Kayaku Co Ltd | Resin composition, soldering resist resin composition and their cured bodies |
| JP5400005B2 (en) * | 2009-09-30 | 2014-01-29 | 関西ペイント株式会社 | Epoxy resin composition and coating composition containing the same |
| KR101521404B1 (en) * | 2011-12-27 | 2015-05-18 | 도레이 카부시키가이샤 | Epoxy resin composition for fiber-reinforced composite materials, prepreg, and fiber-reinforced composite material |
| CN103113604B (en) * | 2013-01-28 | 2015-08-12 | 北京化工大学常州先进材料研究院 | The preparation method of low temperature curing prepreg interlaminar shear strength during a kind of base polyurethane prepolymer for use as improves |
| DE102014013289A1 (en) * | 2014-09-14 | 2016-03-17 | Heiko Klingenberg | Process for the production of a fiber composite material from glass or carbon fibers by coating the fibers with water-dilutable paints before the forming or injection molding process and the further processing of decorative plastic components in the interior and exterior of automobiles and the production of sports equipment or hardboard, as well as the partial fluoroscopy of such objects |
| JP6593636B2 (en) * | 2015-10-29 | 2019-10-23 | Ｄｉｃ株式会社 | Epoxy resin composition for fiber reinforced composite materials |
| CN105440252B (en) * | 2015-12-16 | 2018-03-20 | 广州大学 | A kind of waterborne polyurethane modified epoxy itaconic acid resin of ultraviolet light solidification and preparation method thereof |
| US11203659B2 (en) * | 2016-05-31 | 2021-12-21 | Showa Denko K. K. | Method for producing polyurethane, epoxy carboxylate composition, polyurethane, and polyurethane resin composition |
| CN106543647B (en) * | 2016-11-05 | 2018-10-23 | 北京化工大学 | A kind of high tenacity, low temperature resistant resin matrix and preparation method thereof |
| CN109749409A (en) * | 2018-12-28 | 2019-05-14 | 中水电第十一工程局（郑州）有限公司 | A kind of dedicated ageing-resistant, resistant abrasion ceramic composite of waterwork |
-
2020
- 2020-08-21 CN CN202010852107.4A patent/CN112062924B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112062924A (en) | 2020-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113881006B (en) | Liquid crystal type polyurethane prepolymer for toughening epoxy resin adhesive and preparation method and application thereof | |
| CN113549199B (en) | Bio-based solvent-resistant polyester polyol, polyurethane resin and preparation process thereof | |
| CN111073325A (en) | Lignin/fiber thermoplastic composite material and preparation method thereof | |
| CN111548600A (en) | Modified carbon fiber reinforced thermoplastic resin composite material | |
| CN102504511A (en) | Polyurethane modified unsaturated polyester resin composition and preparation method thereof | |
| CN113667275B (en) | Improved lignin epoxy resin/carbon fiber composite material and preparation method thereof | |
| CN112062924B (en) | Polyurethane resin for winding process, resin/fiber composite material, and preparation method and application thereof | |
| CN112062937B (en) | Carbamate-based epoxy compounds, methods of making, and uses thereof | |
| CN109096505B (en) | Method for improving interfacial property of composite material by grafting polycarboxy polyurethane | |
| CN114133908B (en) | High-strength fast-curing polyurethane adhesive and preparation method thereof | |
| CN116041652A (en) | Biodegradable polyurethane foam material and preparation method thereof | |
| CN111057461B (en) | Preparation method of single-component water-curing polyurethane waterproof coating | |
| CN114560995B (en) | Method for preparing polyurethane from polyester hybrid fibers and application of polyurethane | |
| CN109897161B (en) | Heat-repairing polyurethane elastomer containing ketal structure and preparation method thereof | |
| CN112457470A (en) | Preparation method of polyurethane conveyor belt based on modified graphene | |
| CN1141718C (en) | Liquid polyester modified anticorrosion stress-resistant core rod for high-voltage composite insulator | |
| CN106478924B (en) | A kind of hydrogenated butyronitrile type polyurethane of crosslinking | |
| CN118290783B (en) | Fiber reinforced polyurethane composite material and preparation method thereof | |
| CN112980082B (en) | Socket joint type polyethylene solid wall drain pipe | |
| CN116574359B (en) | Impact-resistant modified epoxy resin and preparation process thereof | |
| CN117384443B (en) | Flame-retardant regenerated plastic and preparation method thereof | |
| CN115536615B (en) | Bio-based epoxy resin precursor, composition, cured product, preparation method and application | |
| CN118325032A (en) | Polyurethane matrix resin and prepreg prepared from same | |
| CN113402852B (en) | Corrosion-resistant lignin epoxy resin/carbon fiber composite material and preparation method thereof | |
| CN114276514B (en) | Polyurethane-acrylic hybrid resin and application 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 |