CN115536798A

CN115536798A - Polyol composition

Info

Publication number: CN115536798A
Application number: CN202110740715.0A
Authority: CN
Inventors: 孙国斌; 李怡青; 梅克·莎拉; 哈根·托斯滕
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2021-06-30
Filing date: 2021-06-30
Publication date: 2022-12-30

Abstract

The invention relates to a polyol composition, a polyurethane reaction system comprising the polyol composition and application of the polyol composition in preparation of a polyurethane composite material.

Description

Polyol composition

Technical Field

Background

The polyol composition in the polyurethane reaction system is very important, and different polyol compositions may bring different physical properties and reaction products. Particularly when used for the production of large parts such as fan blades and parts for ships and the like, it is important whether the polyol composition can bring about satisfactory workability time, uniform and stable filling, and the like.

CN104031229A discloses a polyurethane modified resin for windmill blades and a preparation method thereof, wherein the modified resin is obtained by reacting polyester resin, hydroxyl-containing acrylate and isocyanate and then diluting the reaction product by using an unsaturated monomer.

CN104974502a discloses a polyurethane composite material comprising a polyurethane resin matrix and a reinforcing material, wherein the polyurethane resin matrix is prepared by a polyurethane reaction system comprising: a) An isocyanate component comprising one or more organic polyisocyanates; b) An isocyanate-reactive component.

CN108727550A is a photosensitive resin and its application, the photosensitive resin includes crystallized polyurethane acrylate oligomer, reactive diluent and photoinitiator.

Despite the above disclosures, there is still a great need in the art for more suitable polyol compositions to meet the various needs.

Summary of The Invention

One aspect of the present invention provides a polyol composition comprising:

b1 At least one polyol;

b2 At least one compound having the structure of formula (I)

Wherein R is ₁ Selected from hydrogen, methyl or ethyl; r is ₂ Selected from the group consisting of alkylene having 2 to 6 carbon atoms, 2,2-bis (4-phenylene) -propane, 1,4-bis (methylene) benzene, 1,3-bis (methylene) benzene, 1,2-bis (methylene) benzene; n is an integer selected from 1 to 6;

b3 At least one non-hydroxyl containing multifunctional (meth) acrylate.

Preferably, the b 1) component is selected from one or more organic polyols having a functionality of from 1.7 to 6 and a hydroxyl number of from 150 to 1100mgKOH/g (test method lSO 14900-2017).

Preferably, the b 1) component is present in an amount of 9 to 60wt.%, preferably 10 to 60wt.%, based on the total weight of the polyurethane reaction system.

Preferably, the b 2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.

Preferably, the b 2) component is present in an amount of 3 to 34 wt.%, preferably 5 to 33wt.%, based on the total weight of the polyurethane reaction system.

Preferably, the multifunctional (meth) acrylate containing no hydroxyl group refers to a substance containing no hydroxyl group but two or more (meth) acrylate groups in the molecular structure.

Preferably, the b 3) component is selected from ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,2,3-glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, or any combination thereof.

Preferably, the b 3) component is present in an amount of 1.8 to 42 wt.%, preferably 2.2 to 36.1 wt.%, more preferably 2.47 to 20.1 wt.%, particularly preferably 2.8 to 18.8 wt.%, more particularly preferably 3.8 to 17.6 wt.%, based on the total weight of the polyol composition.

Surprisingly, we have found that the polyol compositions of the present invention comprising a non-hydroxyl containing multifunctional (meth) acrylate, together with a polyol compatible therewith and a compound having the structure of formula (I), extend the open time of the corresponding polyurethane reaction system, thereby enabling sufficient open time to be obtained when preparing polyurethane resins or composites. To achieve a uniform and sound filling of the prepared components, in particular large components, such as fan blades, ships, etc. Thereby improving the yield and the production efficiency, reducing or avoiding the waste of raw materials and being more environment-friendly.

In another aspect of the present invention, there is provided a polyurethane reaction system comprising:

component A) comprising: at least one polyisocyanate;

component B) comprising:

b1 At least one polyol;

b2 At least one compound having the structure of formula (I)

Wherein R is ₁ Selected from hydrogen, methyl or ethyl; r ₂ Selected from the group consisting of alkylene having 2 to 6 carbon atoms, 2,2-bis (4-phenylene) -propane, 1,4-bis (methylene) benzene, 1,3-bis (methylene) benzene, 1,2-bis (methylene) benzene; n is an integer selected from 1 to 6;

b3 At least one non-hydroxyl containing multifunctional (meth) acrylate;

component C) a free-radical reaction initiator.

Preferably, the b 1) component is selected from one or more organic polyols having a functionality of from 1.7 to 6 and a hydroxyl number of from 150 to 1100mg KOH/g (test method ISO 14900-2017).

Preferably, the b 1) component is present in an amount of 10 to 60wt.%, preferably 20 to 60wt.%, based on the total weight of the polyurethane reaction system.

Preferably, the b 3) component is present in an amount of 1 to 18 wt.%, preferably 1.2 to 16 wt.%, more preferably 1.3 to 9.6 wt.%, particularly preferably 1.5 to 9 wt.%, more particularly preferably 2 to 8.5 wt.%, based on the total weight of the polyurethane reaction system.

Preferably, the polyurethane reaction system has a workable time of 68 minutes or more, preferably 70 minutes or more, more preferably 72 minutes or more, and particularly preferably 80 minutes or more at 35 ℃.

Preferably, the polyurethane reaction system comprising component b 3) has an increase in the open time at 35 ℃ of more than or equal to 5%, preferably more than or equal to 10%, more preferably more than or equal to 15% compared to a polyurethane reaction system not comprising component b 3).

Preferably, the linear shrinkage of the polyurethane reaction system is less than or equal to 0.95%, preferably less than or equal to 0.90%, more preferably less than or equal to 0.80% (test method lSO 2577-2007).

Surprisingly, it has been found that the polyurethane reaction system of the present invention, which comprises the polyol composition of each of components b 1) to b 3), the isocyanate and the radical reaction initiator, not only can produce polyurethane products with excellent quality, but also can bring about longer operable time, and the polyurethane reaction system can gain enough operable time for the uniform filling and curing of the products for preparing the polyurethane products, especially polyurethane products with larger sizes, such as fan blades, ships and the like.

In another aspect of the invention, the invention provides an application of the polyurethane reaction system in the preparation of fan blades.

The polyurethane reaction system comprises:

component A) comprising: at least one polyisocyanate;

component B) comprising:

b1 At least one polyol;

b2 At least one compound having the structure of formula (I)

b3 At least one non-hydroxyl containing multifunctional (meth) acrylate;

component C) a free-radical reaction initiator.

In still another aspect of the present invention, there is provided a polyurethane resin prepared by reacting the polyurethane reaction system of the present invention.

In another aspect of the present invention, a method for preparing a polyurethane composite material is provided, wherein the polyurethane composite material is prepared by mixing the following components:

the polyurethane reaction system of the invention; and (c) and (d),

at least one reinforcing material.

Preferably, the polyurethane composite is prepared by a pultrusion process, a winding process, a hand lay-up process, a vacuum infusion process, a spray forming process or a combination thereof.

Preferably, the reinforcing material of the present invention refers to a material including glass fibers, carbon nanotubes, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, hard particles, metal fibers, or a combination thereof.

Preferably, the method comprises the simultaneous presence of a free radical polymerization reaction and an addition polymerization reaction of isocyanate groups and hydroxyl groups.

Preferably, the polyurethane reaction system comprising component b 3) has an increase in the open time at 35 ℃ of more than or equal to 5%, preferably more than or equal to 10%, compared to a polyurethane reaction system not comprising component b 3).

Preferably, the linear shrinkage of the polyurethane reaction system is less than or equal to 0.95%, preferably less than or equal to 0.90%, more preferably less than or equal to 0.80% (test method ISO 2577-2007).

In still another aspect of the present invention, there is provided a polyurethane composite material prepared by the method for preparing a polyurethane composite material according to the present invention.

Preferably, the reinforcing material content of the polyurethane composite is equal to or greater than 40wt%, preferably equal to or greater than 45wt%, more preferably 50-88wt%, based on the total weight of the polyurethane composite.

In a further aspect of the present invention, there is provided a polyurethane product comprising the polyurethane resin of the present invention, wherein the polyurethane product is selected from cable bridges, curtain wall frames for doors and windows, ladder frames, tent poles or tubes, antiglare sheets, floors, sucker rods, utility poles and crossarms, guardrails, grilles, structural sections for buildings, container sections and sheets, bicycle frames, fishing rods, cable cores, insulator mandrels, radomes, single-layer or sandwich continuous sheets, fan blades and parts thereof, nacelle covers for wind turbines, propeller blades, hull casings for ships, vehicle interior and exterior and hull, radar covers, structural member materials for mechanical equipment, and trim and structural parts for buildings and bridges, preferably fan blades or parts thereof, nacelle covers for wind turbines, more preferably blade shells, webs, beam caps, girders, auxiliary beams, and blade roots for fan blades.

Detailed Description

I. Polyol composition

The present invention provides a polyol composition comprising:

b1 At least one polyol;

b2 At least one compound having the structure of formula (I)

b3 At least one non-hydroxyl containing polyfunctional (meth) acrylate.

Polyurethane reaction System

The polyurethane reaction system of the present invention comprises:

component A) comprising: at least one polyisocyanate;

component B) comprising:

b1 At least one polyol;

b2 At least one compound having the structure of formula (I)

b3 At least one non-hydroxyl containing multifunctional (meth) acrylate;

component C) a free-radical reaction initiator.

In embodiments of the present invention, the organic polyisocyanate may be any aliphatic, cycloaliphatic, or aromatic isocyanate known for use in the preparation of polyurethanes. Examples include, but are not limited to: toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenyl methane polyisocyanate (pMDI), 1,5-Naphthalene Diisocyanate (NDI), hexamethylene Diisocyanate (HDI), methylcyclohexyl diisocyanate (TDI), 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyldimethylene diisocyanate (TMXDI), and polymers thereof or combinations thereof. The isocyanates which can be used according to the invention preferably have a functionality of from 2.0 to 3.5, particularly preferably from 2.1 to 2.9. The isocyanate viscosity is preferably from 5 to 700 mPas, particularly preferably from 10 to 300 mPas, determined at 25 ℃ in accordance with DIN 53019-1-3.

When used in the present invention, the organic polyisocyanate includes an isocyanate dimer, trimer, tetramer, pentamer or a combination thereof.

In a preferred embodiment of the present invention, the isocyanate component a) is selected from the group consisting of diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (pMDI), and polymers, prepolymers or combinations thereof.

Blocked isocyanates may also be used as isocyanate component a), which may be prepared by reacting an excess of an organic polyisocyanate or mixtures thereof with a polyol compound. These compounds and their preparation are well known to those of ordinary skill in the art.

Preferably, the organic polyisocyanates of the present invention have an NCO content of 20 to 33wt.%, preferably 25 to 32wt.%, particularly preferably 30 to 32wt.%. The NCO content was determined by GB/T12009.4-2016.

Preferably, the organic polyisocyanates can also be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers can be obtained by reacting an excess of the above-mentioned organic polyisocyanate with a compound having at least two isocyanate-reactive groups at a temperature of, for example, 30 to 100 c, preferably about 80 c. The NCO content of the polyisocyanate prepolymers of the present invention is from 20 to 33% by weight, preferably from 25 to 32% by weight. The NCO content was determined by GB/T12009.4-2016.

Preferably, the polyisocyanate of the present invention is present in an amount of 65wt.% or less, preferably 60wt.% or less, more preferably 30 to 45 wt.%, based on the total weight of the polyurethane reaction system.

In an embodiment of the invention, the isocyanate-reactive component comprises one or more organic polyols b 1). The organic polyol is present in an amount of 9 to 60wt.%, based on 100wt.% of the total weight of the polyurethane reaction system. The organic polyol may be an organic polyol commonly used in the art for making polyurethanes, including but not limited to: polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols, polymer polyols, vegetable oil based polyols, or combinations thereof.

The polyether polyols may be prepared by known processes, for example, by reacting an olefin oxide with an initiator in the presence of a catalyst. The catalyst is preferably, but not limited to, alkali hydroxide, alkali alkoxide, antimony pentachloride, boron fluoride etherate, or a mixture thereof. The olefin oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, or mixtures thereof, with ethylene oxide and/or propylene oxide being particularly preferred. The initiator is preferably, but not limited to, a polyol, preferably, but not limited to, water, ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, trimethylolpropane, glycerol, bisphenol a, bisphenol S, or mixtures thereof, or a polyamine, preferably, but not limited to, ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, diethylenetriamine, tolylenediamine, or mixtures thereof.

The polyether carbonate polyols, which can be prepared by addition of carbon dioxide and alkylene oxides onto starters containing active hydrogen using double metal cyanide catalysts, can also be used in the present invention.

The polyester polyol is prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyhydric alcohol. The dicarboxylic acid is preferably, but not limited to, an aliphatic carboxylic acid having 2 to 12 carbon atoms, and the aliphatic carboxylic acid having 2 to 12 carbon atoms is preferably, but not limited to, succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane carboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, or a mixture thereof. The dicarboxylic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, or a mixture thereof. The polyhydric alcohol reacted with the dicarboxylic acid or dicarboxylic acid anhydride is preferably, but not limited to, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-methylpropanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or mixtures thereof. The polyester polyol also comprises polyester polyol prepared from lactone. The polyester polyol prepared from a lactone is preferably, but not limited to, epsilon-caprolactone. Preferably, the polyester polyols have a molecular weight of 200 to 3000 and a functionality of 2 to 6, preferably 2 to 4, more preferably 2 to 3.

The polycarbonate diol can be prepared by reacting dihydric alcohol with dialkyl carbonate or diaryl carbonate or phosgene. The dihydric alcohol is preferably, but not limited to, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, trioxymethylene glycol, or mixtures thereof. The dialkyl carbonate or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.

When used in the present invention, the vegetable oil-based polyol includes vegetable oil, vegetable oil polyol or a modified product thereof. Vegetable oils are compounds prepared from unsaturated fatty acids and glycerol or oils extracted from fruits, seeds, germs of plants, preferably but not limited to peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, palm oil. The vegetable oil polyol is a polyol initiated by one or more vegetable oils. Synthetic vegetable oil polyol starters include, but are not limited to, soybean oil, palm oil, peanut oil, canola oil, and castor oil. The vegetable oil polyol starter may be used to introduce hydroxyl groups by cleavage, oxidation, or transesterification, and the corresponding vegetable oil polyol may be prepared by processes well known to those skilled in the art for preparing organic polyols.

Methods for measuring hydroxyl numbers are well known to the person skilled in the art, for example in Houben Weyl, methoden der Organischen Chemie, vol.XIV/2 Makromolekulare Stoffe, p.17, georg Thieme Verlag; stuttgart 1963. The entire contents of this document are incorporated herein by reference.

When used in the present invention, unless otherwise indicated, the functionality, hydroxyl number of the organic polyol all refer to the average functionality and average hydroxyl number.

In an embodiment of the invention, the isocyanate-reactive component further comprises one or more compounds b 2) having the structure of formula (I)

Wherein R is ₁ Selected from hydrogen, methyl or ethyl; r ₂ Selected from alkylene groups having 2 to 6 carbon atoms; n is an integer selected from 1 to 6.

In a preferred embodiment of the invention, R ₂ Selected from the group consisting of ethylene, propylene, butylene, pentylene, 1-methyl-1,2-ethylene, 2-methyl-1,2-ethylene, 1-ethyl-1,2-ethylene, 2-ethyl-1,2-ethylene, 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 3-methyl-1,3-propylene, 1-ethyl-1,3-propylene, 2-ethyl-1,3-propylene, 3-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-5623-butylene and 4-methyl-325723-butylene, 325756-butyl 6256-butylene, bis (phenylene-phenyl) -323849-phenylene-bis (diphenylene-phenyl) -345749, bis (phenylene-325756).

In a preferred embodiment of the invention, the b 2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.

The compounds of formula (I) can be prepared by methods customary in the art, for example by (meth) acrylic anhydride or (meth) acrylic acid, (meth) acryloyl halide compounds with HO- (R) ₂ O) _n H is throughEsterification reaction preparation, which is well known to the person skilled in the art, for example as described in handbook of polyurethane raw materials and auxiliaries (Liu Yijun, published 4/1/2005) chapter three and polyurethane elastomers (Liu Houjun, published 8/2012) chapter two, the entire contents of which are incorporated herein by reference.

The polyfunctional (meth) acrylate having no hydroxyl group according to the present invention means a substance having no hydroxyl group in the molecular structure but having two or more (meth) acrylate groups.

Preferably, the multifunctional (meth) acrylate having no hydroxyl group, b 3) component is selected from ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,2,3-glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, or any combination thereof.

After repeated experiments, we have surprisingly found that the polyol composition of the present invention, which comprises a multifunctional (meth) acrylate containing no hydroxyl group, and a polyol and a compound having the structure of formula (I) adapted thereto, can prolong the operable time of the corresponding polyurethane reaction system, and at the same time, the linear shrinkage rate can be increased. However, if the linear shrinkage exceeds a certain value, the requirement for a particular application may not be satisfied. In a preferred embodiment of the present invention, a polyurethane reaction system comprising a specific content of a hydroxyl-free polyfunctional (meth) acrylate and other components compatible therewith can achieve an extension of the workable time and an increase in linear shrinkage to a preferred range that satisfies certain requirements.

In an embodiment of the invention, the polyurethane reaction system further comprises C) a free radical reaction initiator. The free radical initiator used in the present invention may be added to either the polyol component or the isocyanate component or both components. These initiators include, but are not limited to, peroxides, persulfides, peroxycarbonates, peroxyboric acids, azo compounds, or other suitable free radical initiators that can initiate curing of double bond containing compounds, examples of which include t-butyl peroxyisopropylcarbonate, t-butyl peroxy-3,5,5-trimethylhexanoate, methyl ethyl ketone peroxide, cumene hydroperoxide.

The free radical reaction initiator is typically present in an amount of 0.1 to 8wt.%, based on 100wt.% of the total weight of the isocyanate-reactive components. In addition, an accelerator, such as a cobalt compound or an amine compound, may be present.

In embodiments of the present invention, the polyurethane reaction system may further comprise a catalyst for catalyzing the reaction of isocyanate groups (NCO) with hydroxyl groups (OH). Suitable catalysts for the polyurethane reaction are preferably, but not limited to, amine catalysts, organometallic catalysts, or mixtures thereof. The amine catalyst is preferably, but not limited to, triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, N, N, N ', N' -tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, N, N-methylaniline, N, N-dimethylaniline, or a mixture thereof. The organometallic catalyst is preferably, but not limited to, organotin compounds, such as: tin (II) acetate, tin (II) octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate, dioctyltin diacetate, or mixtures thereof. The catalyst is used in an amount of 0.001 to 10wt.%, based on 100wt.% of the total weight of the isocyanate-reactive component.

In the present example, the polyurethane reaction, i.e., the polyaddition of isocyanate groups, which may be isocyanate groups contained in the organic polyisocyanate (component a), which may also be isocyanate groups contained in the reaction intermediate of the organic polyisocyanate (component a) with the organic polyol (b 1) component) or b 2) component, with hydroxyl groups, which may be hydroxyl groups contained in the organic polyol (b 1) component) or b 2) component, which may also be hydroxyl groups contained in the reaction intermediate of the organic polyisocyanate (component a) with the organic polyol (b 1) component) or b 2) component, is carried out.

In the present embodiment, the radical polymerization is an addition polymerization of olefinic bonds, wherein the olefinic bonds may be those contained in component b 2) or those contained in the intermediate product of the reaction of component b 2) with the organic polyisocyanate.

In the present examples, the polyurethane addition polymerization (i.e., the addition polymerization of isocyanate groups with hydroxyl groups) occurs simultaneously with the free radical polymerization. As known to those skilled in the art, suitable reaction conditions can be selected so that the polyurethane addition polymerization reaction and the free radical polymerization reaction are carried out in sequence, but the polyurethane matrix prepared in the way is different from the polyurethane resin matrix prepared by simultaneously carrying out the polyurethane addition polymerization reaction and the free radical polymerization reaction, so that the mechanical properties and the manufacturability of the prepared polyurethane composite material are different.

In an embodiment of the present invention, the polyurethane reaction system may further comprise auxiliaries or additives, including but not limited to: fillers, internal mold release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, defoamers, coupling agents, surface wetting agents, leveling agents, water scavengers, catalysts, molecular sieves, thixotropic agents, plasticizers, blowing agents, foam stabilizers, free radical reaction inhibitors, or combinations thereof, which may optionally be included in the isocyanate component a) and/or the isocyanate-reactive component B). These components can also be stored separately as component D) and, when used for the preparation of polyurethane composites, are mixed with the isocyanate component A) and/or the isocyanate-reactive component B) before the preparation.

In some embodiments of the invention, the filler is selected from: aluminum hydroxide, bentonite, fly ash, wollastonite, perlite powder, cenosphere, calcium carbonate, talcum powder, mica powder, porcelain clay, fumed silica, expandable microspheres, diatomite, volcanic ash, barium sulfate, calcium sulfate, glass microspheres, stone powder, wood powder, sawdust, bamboo powder, bamboo sawdust, rice grains, straw scraps, sorghum straw scraps, graphite powder, metal powder, thermosetting composite material recycled powder, plastic particles or powder or a combination thereof. Wherein the glass microspheres can be solid or hollow.

The internal mold release agent which can be used in the present invention includes any conventional mold release agent used for producing polyurethane, and examples thereof include long-chain carboxylic acids, particularly fatty acids such as stearic acid, amines of long-chain carboxylic acids such as stearamide, fatty acid esters, metal salts of long-chain carboxylic acids such as zinc stearate, or polysiloxanes.

Examples of flame retardants that can be used in the present invention include triaryl phosphates, trialkyl phosphates, triaryl phosphates or trialkyl phosphates with halogen, melamine resins, halogenated paraffins, red phosphorus, or combinations thereof.

Other adjuvants useful in the present invention include water scavengers such as molecular sieves; defoamers, such as polydimethylsiloxane; coupling agents, such as monoepoxyethane or organic amine functional trialkoxysilane or combinations thereof. Coupling agents are particularly preferred for improving the adhesion of the resin matrix to the fibrous reinforcement. Finely particulate fillers, such as clays and fumed silicas, are commonly used as thixotropic agents.

The radical reaction inhibitor which can be used in the present invention includes polymerization inhibitors and retarders, etc., such as some phenols, quinone compounds or hindered amine compounds, examples of which include methylhydroquinone, p-methoxyphenol, benzoquinone, polymethine piperidine derivatives, low valent copper ions, etc.

Preparation of polyurethane composite

In another aspect of the present invention, there is provided a method for preparing a polyurethane composite comprising a polyurethane resin matrix and a reinforcing material, the method comprising the step of preparing the polyurethane resin matrix under reaction conditions such that a polyurethane reaction system, as described above, is simultaneously subjected to a radical polymerization reaction and a reaction of isocyanate groups with hydroxyl groups.

In the present examples, the polyurethane addition polymerization (i.e., the addition polymerization of isocyanate groups with hydroxyl groups) occurs simultaneously with the free radical polymerization.

The polyurethane composite material can be prepared by a polyurethane vacuum infusion process. The method of operation of the polyurethane vacuum infusion process is well known to those skilled in the art, for example, as described in patent CN 1954995a, the entire disclosure of which is incorporated herein by reference.

In the vacuum infusion process, one or more core materials are provided in a mould, which core materials are optionally covered in whole or in part by a reinforcement material. Then, forming negative pressure in the mould to enable the polyurethane resin to be poured into the mould; before curing, the polyurethane resin will fully wet the reinforcement material and the core material will be fully or partially wetted by the polyurethane resin. And then, adopting proper conditions to simultaneously carry out polyurethane addition polymerization reaction and free radical polymerization reaction on the polyurethane resin, so that the polyurethane resin is cured to form a polyurethane resin matrix. In the above vacuum infusion process, the mold may be a mold commonly used in the art, and a person skilled in the art may select a suitable mold according to the properties and dimensions required for the final product. To ensure sufficient operating time for the preparation of large articles using a vacuum infusion process, it is necessary to maintain the resin at a sufficiently low viscosity during infusion so that good flowability is maintained. If the viscosity is higher than 600mPas, the viscosity of the resin is considered to be too high to cause the flowability to be poor and is not suitable for the vacuum infusion process.

The core material is used together with the polyurethane resin matrix and the reinforcing material, so that the molding of the composite material is facilitated and the weight of the composite material is reduced. The polyurethane composite of the present invention may use a core material commonly used in the art, examples of which include, but are not limited to, polystyrene foams, such as

Foaming; polyester PET foam; polyimide PMI foam; polyvinyl chloride foam; metal foams, such as those available from Mitsubishi corporation; balsa wood (balsa wood), and the like.

Preferably, the polyurethane reaction system is suitable for being used in a polyurethane vacuum infusion process to prepare a polyurethane composite material, has longer operable time, and the polyurethane composite material prepared by the polyurethane vacuum infusion process has good mechanical properties, particularly higher heat distortion temperature, thereby solving the problem that the operable time of the polyurethane reaction system and the heat distortion temperature of the prepared polyurethane composite material cannot be simultaneously improved in the prior art. The polyurethane composite material can be used for preparing wind driven generator blades, wind driven generator cabin covers, ship blades, ship shells, interior and exterior trimming parts and shells of vehicles, radar covers, structural part materials of mechanical equipment, and trimming parts and structural parts of buildings and bridges.

The polyurethane composites of the present invention can also be prepared by pultrusion processes, winding processes, hand lay-up processes, spray forming processes or combinations thereof for a detailed description of these processes, see chapters 2 and 6-9 of composite processes and equipment (Liu Xiongya et al, 1994, published by the university of Wuhan Engineers). The entire disclosure of which is incorporated herein by reference.

The invention is further illustrated below with reference to specific examples. It is to be understood, however, that these examples are illustrative only and are not to be construed as limiting the scope of the present invention.

Examples

Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.

pbw refers to the mass parts of each component of the polyurethane reaction system;

functionality, means according to the industry formula: functionality = hydroxyl value/56100; wherein the molecular weight is determined by GPC high performance liquid chromatography;

the operable time (pot-life) is the time from the stirring of the components of the reaction system until the viscosity of the mixture reaches 600mPa.S. Can be determined by the following method: keeping the temperature of each component of a polyurethane reaction system constant at 35 ℃, then mixing the components in proportion, stirring for 1 minute until the components are uniform, keeping the temperature at 35 ℃, measuring the viscosity every 3 minutes, and recording the viscosity as the operable time (pot-life) when the viscosity reaches 600mPa.S. The viscometer is a Brook-Field product, model DV2TLTJ0.

Linear shrinkage, which refers to the linear shrinkage of the resin produced by the reaction of the polyurethane reaction system measured according to test standard ISO 2577-2007. The specific method of the invention can be as follows: the components of the polyurethane reaction system are proportioned according to the proportion, the mixture is placed into a semi-cylinder mould preheated to 35 ℃ in an oven, the length h1 of the liquid level in the semi-cylinder mould is recorded, then the temperature is uniformly and slowly raised to 70 ℃ within 2 hours, and then the temperature is kept at 70 ℃ for 4 hours. After cooling to room temperature (e.g., 25 ℃), the length h2 of the polyurethane resin is measured, and the linear shrinkage = (h 1-h 2)/h 1X 100% is measured and calculated.

Isocyanate index, which means a value calculated by the following formula:

the raw materials used in the examples are as follows:

isocyanate: desmodur 1511l, nco wt.%:30.5-32.5wt.%, viscosity at 25 ℃:160-240mP.s, available from Corcission Polymer (China) Ltd;

radical reaction initiator: tert-butyl peroxybenzoate (TBPB), available from Ak Su Nuobei mol;

accelerator (b): NL-49P, available from Ak Su Nuobei mol;

polyol: propylene oxide based polyether polyol, initiator glycerol, functionality =3, hydroxyl value 350mgKOH/g, purchased from kostew polymers (china) ltd;

hydroxypropyl methacrylate (HPMA): procurement from Heshi wall chemical;

1,6-hexanediol diacrylate (HDDA): purchased from alatin;

trimethylolpropane trimethacrylate (TMPTMA): purchased from aladine.

Examples E1-4 and comparative example C1

Preparing a white material (component B): according to the component proportion in the table 1, the polyol, the HPMA and the NL-49P, HDDA are weighed, sequentially added into a plastic cup, uniformly stirred and then placed into a 35 ℃ oven for constant temperature.

Preparing a black material (component A): according to the component proportion in the table 1, TBPB and 1511L are weighed, added into another plastic cup in sequence, stirred uniformly, and placed into a 35 ℃ oven for constant temperature.

The black and white materials were quickly weighed according to the ratio in table 1, placed in a new plastic cup and quickly stirred uniformly (total weight of black and white materials 300 g). Then, the mixture was placed in a water bath at 35 degrees centigrade, the change in viscosity with time and temperature was monitored, and the operable time was measured.

Linear shrinkage was measured according to test standard ISO2577-2007 and the procedure described above.

The test results are shown in Table 1.

TABLE 1 quality fractions of the components of examples E1 to 4 and comparative example C1 and test results (unit: quality fraction bpw)

	C1	E1	E2	E3	E4
						Polyhydric alcohols	60	60	60	60	60
HPMA	40	40	40	40	40
						NL-49P	0.1	0.1	0.1	0.1	0.1
HDDA		10	15	25	35

1511L	87	87	87	87	87
						TBPB	1.6	1.6	1.6	1.6	1.6

						Operable time (35 deg.C)	67	85	99	126	155
Linear shrinkage rate	0.65％	0.65％	0.65％	0.71％	0.75％

As can be seen from the experimental results in table 1, examples 1 to 4, to which HDDA was added, can significantly extend the operable time and increase the linear shrinkage rate, compared to comparative example 1. Based on different applications, the proper mass ratio of each component can be selected to achieve the balance of operable time and linear shrinkage rate so as to meet different requirements.

Examples E5 to 8 and comparative example C1

Preparing a white material (component B): according to the component proportion in the table 2, the polyol, HPMA and NL-49P, TMPTMA are weighed, sequentially added into a plastic cup, uniformly stirred and then placed into a 35 ℃ oven for constant temperature.

Preparation of black materials (component A): according to the component proportion in the table 2, TBPB and 1511L are weighed, added into another plastic cup in sequence, stirred uniformly, and placed into a 35 ℃ oven for constant temperature.

According to the component proportion in the table 2, the black and white materials are quickly weighed and put into a new plastic cup to be quickly and uniformly stirred (the total weight of the black and white materials is 300 g). Then, the mixture was placed in a water bath at 35 degrees centigrade, the change in viscosity with time and temperature was monitored, and the operable time was measured.

Linear shrinkage was measured according to test standard ISO2577-2007 and the procedure described previously.

The test results are shown in Table 1.

TABLE 2 test results for examples E5-8 and comparative example C1

	C1	E5	E6	E7	E8
						Polyhydric alcohols	60	60	60	60	60
HPMA	40	40	40	40	40
						NL-49P	0.1	0.1	0.1	0.1	0.1
TMPTMA		10	15	25	35

1511L	87	87	87	87	87
						Tc	1.6	1.6	1.6	1.6	1.6

						Operable time (35 deg.C)	67	82	82	99	110
Linear shrinkage rate	0.65％	0.66％	0.66％	0.69％	0.78％

As can be seen from table 2, the working time of examples 5 to 8 to which TMPTMA was added was significantly extended and at the same time, the linear shrinkage thereof was also increased, compared to comparative example 1. The proper mass ratio of each component can be selected to achieve the balance of operable time and linear shrinkage rate so as to meet different requirements.

Claims

1. A polyol composition comprising:

b1 At least one polyol;

b2 At least one compound having the structure of formula (I)

b3 At least one non-hydroxyl containing multifunctional (meth) acrylate.

2. The polyol composition of claim 1 wherein the b 3) component is selected from the group consisting of ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,2,3-glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and combinations thereof.

3. The polyol composition of claim 1 or 2, wherein the b 3) component is present in an amount of 1.8 to 42 wt.%, preferably 2.2 to 36.1 wt.%, more preferably 2.47 to 20.1 wt.%, particularly preferably 2.8 to 18.8 wt.%, more particularly preferably 3.8 to 17.6 wt.%, based on the total weight of the polyol composition.

4. A polyurethane reaction system comprising:

component A) comprising: at least one polyisocyanate;

component B) comprising:

b1 At least one polyol;

b2 At least one compound having the structure of formula (I)

b3 At least one non-hydroxyl containing multifunctional (meth) acrylate;

component C), a free-radical reaction initiator.

5. The polyurethane reaction system according to claim 4, wherein the b 3) component is present in an amount of 1 to 18 wt.%, preferably 1.2 to 16 wt.%, more preferably 1.3 to 9.6 wt.%, particularly preferably 1.5 to 9 wt.%, more particularly preferably 2 to 8.5 wt.%, based on the total weight of the polyurethane reaction system.

6. Polyurethane reaction system according to claim 4 or 5, characterised in that the polyurethane reaction system has a working time at 35 ℃ of 68 minutes or more, preferably 70 minutes or more, more preferably 72 minutes or more, particularly preferably 80 minutes or more.

7. Polyurethane reaction system according to any of claims 4 to 6, characterized in that the operable time at 35 ℃ of the polyurethane reaction system comprising component b 3) is increased by more than or equal to 5%, preferably more than or equal to 10%, more preferably more than or equal to 15% compared to a polyurethane reaction system not comprising component b 3).

8. Polyurethane reaction system according to any of claims 4 to 7, characterised in that the linear shrinkage of the polyurethane reaction system is less than or equal to 0.95%, preferably less than or equal to 0.90%, more preferably less than or equal to 0.80% (test method ISO 2577-2007).

9. A polyurethane resin obtained by reacting the polyurethane reaction system according to any one of claims 4 to 8.

10. Use of the polyurethane reaction system according to any one of claims 4 to 8 for the production of fan blades.

11. A method for preparing a polyurethane composite material is to mix the following components to prepare the polyurethane composite material:

the polyurethane reaction system of any one of claims 4-8; and the combination of (a) and (b),

at least one reinforcing material.

12. The method according to claim 11, wherein the polyurethane composite is prepared by a pultrusion process, a winding process, a hand lay-up process, a vacuum infusion process, a spray forming process or a combination thereof, preferably by a pultrusion process and/or a vacuum infusion process.

13. A process according to claim 11 or 12, characterized in that it comprises a simultaneous free-radical polymerization and polyaddition of isocyanate groups to hydroxyl groups.

14. Process according to any one of claims 11 to 13, characterised in that the polyurethane reaction system is operable at 35 ℃ for a time of 68 minutes or more, preferably 70 minutes or more, more preferably 72 minutes or more, particularly preferably 80 minutes or more.

15. The process according to any of claims 11 to 14, characterized in that the polyurethane reaction system comprising component b 3) has an increase in the open time at 35 ℃ of more than or equal to 5%, preferably more than or equal to 10%, compared to a polyurethane reaction system not comprising component b 3).

16. The process as claimed in any of claims 11 to 15, wherein the polyurethane reaction system has a linear shrinkage of 0.95% or less, preferably 0.90% or less, more preferably 0.80% or less (test method ISO 2577-2007).

17. A polyurethane composite obtained by the method for producing a polyurethane composite according to any one of claims 11 to 16.

18. Polyurethane composite according to claim 17, characterized in that the reinforcing material content of the polyurethane composite is ≥ 40 wt.%, preferably ≥ 45 wt.%, more preferably 50-88 wt.%, based on the total weight of the polyurethane composite.

19. A polyurethane product comprising the polyurethane resin of claim 9, wherein the polyurethane product is selected from the group consisting of cable trays, curtain wall frames for doors and windows, ladder frames, tent poles or tubes, antiglare panels, floors, sucker rods, utility poles and crossarms, guardrails, grilles, architectural profiles, container profiles and sheets, bicycle frames, fishing poles, cable cores, insulator mandrels, radome, single or sandwich continuous sheets, wind turbine blades and components thereof, wind turbine nacelle covers, ship blades, ship hulls, interior and exterior trim and housings for vehicles, radar covers, structural materials for mechanical equipment, structural trim and structural components for buildings and bridges, preferably wind turbine blades or components thereof, wind turbine nacelle covers, more preferably blade shells, webs, beam caps, girders, joists and blade roots for wind turbine blades.