CN105331088A - Pultrusion PU (polyurethane) resin composite material and preparation method thereof - Google Patents
Pultrusion PU (polyurethane) resin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of pultrusion PU (polyurethane) resin, in particular to a pultrusion PU resin composite material and a preparation method thereof. According to the pultrusion PU resin composite material, reinforced fibers and PU resin in a proper ratio are adopted, wherein the PU resin adopts aliphatic isocyanates to replace conventional aromatic isocyanates, further, primary hydroxyl polyether or primary hydroxyl polyester capable of improving mechanical strength of aliphatic PU and having a terminal group capable of reacting with isocyanates is added to form prepolymers, primary hydroxyl polyether or primary hydroxyl polyester having the terminal group capable of reacting with the isocyanates can improve the mechanical strength of aliphatic PU, and the aliphatic isocyanates have low probability of photooxidation, so that the service life of the composite material in wild and outdoor application is prolonged.
Description
Technical field
The present invention relates to pultrusion polyurethane resin technical field, particularly relate to matrix material of a kind of pultrusion polyurethane resin and preparation method thereof.
Background technology
Pultrusion composite materials is composited by various resin and high-performance fiber pultrusion, and existing pultrusion resin comprises unsaturated polyester, epoxy resin, urethane etc.Unsaturated polyester mechanical property is poor, can not be applied to the occasion that some mechanical property requirements are high, and solidifying agent is superoxide, inflammable and explosive, and processing has certain danger.Epoxy resin is high performance resin, but it is expensive, and curing speed is slow, and due to its degree of crosslinking too high, material is firmly crisp, and toughness is not enough.And in traditional polyurethane resin systems, phenyl ring in a large amount of aromatic isocyanates is under the impact of long-term ultraviolet lighting and high temperature, very easily there is isomery in benzene ring structure, and further by photoxidation, hard section benzene ring structure is destroyed, the intensity of whole molecule can decline to a great extent, thus have impact on the mechanical strength of whole matrix material, greatly limit compound polyurethane material in the wild with outdoor application (such as solar bracket, electric pole, sash, cable bearer etc.), and decrease the work-ing life of compound polyurethane material.
Summary of the invention
The invention provides matrix material of a kind of pultrusion polyurethane resin and preparation method thereof, in order to improve the anti-photooxidation ability of the matrix material of pultrusion polyurethane resin, and then extend its work-ing life.
First the present invention provides a kind of matrix material of pultrusion polyurethane resin, and comprise fortifying fibre and urethane resin that weight ratio is 75-90: 10-25, wherein, described urethane resin is polymerized by Isocyanate prepolymers body, wherein:
Based on the gross weight of described Isocyanate prepolymers body, it is that the aliphatic isocyanates of 60%-100% and weight fraction are the mechanical strength of the improved aliphatic polyurethane of 0%-40% and have the performed polymer that can be formed with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester that described Isocyanate prepolymers body comprises by weight fraction.
In technical solution of the present invention, aliphatic isocyanates is used to instead of existing aromatic isocyanate, and add and high performancely improve the mechanical strength of aliphatic polyurethane and have and can define performed polymer with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester, because aliphatic isocyanic ester not easily photoxidation occurs, therefore extend its in the wild with outdoor application time work-ing life, in addition, having in performed polymer can improve the strength and toughness of aliphatic polyurethane with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester, therefore compensate for the defect of intensity not as aromatic urethane of aliphatic urethane.In addition, by a certain amount of have can with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester, with aliphatic isocyanates pre-polymerization, to improve in pultrusion process under normal temperature the wetting capacity of fortifying fibre.
Preferably, describedly improve the mechanical strength of aliphatic polyurethane and have and can be selected from polytetrahydrofuran (PTMG), polytetrahydrofuran polycaprolactone block polymer (7201A) and polyester diol with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester.
Preferably, described aliphatic isocyanates is selected from isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI).Preferably, the functionality of described aliphatic isocyanates is 2, NCO% is 5%-30%.
Preferably, described Isocyanate prepolymers body is the performed polymer that performed polymer, HDI and polyester diol that performed polymer, HDI and 7201A that performed polymer, IPDI and polyester diol that performed polymer, IPDI and 7201A that IPDI and PTMG is formed are formed are formed are formed are formed, wherein, the functionality of described aliphatic isocyanates is 2, NCO% is 5%-30%.Wherein, IPDI is referred to as isophorone diisocyanate, and chemical name is 3-isocyanic ester methylene-3,5,5-trimethylcyclohexylisocyanate (3-Isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate), purchased from German Bayer AG; HDI is hexamethylene diisocyanate (HexamethyleneDiisocyanate), purchased from German Bayer AG; Polyester diol can be poly adipate succinic acid ester-1000 for poly-hexanodioic acid fourth diester dibasic alcohol PBA, PBA1000, purchased from Changxing, Taiwan Chemical Co., Ltd.; 7201A is polytetrahydrofuran polycaprolactone block polymer, and purchased from Sweden's Paasche holder, model is capa7201A; PTMG is polytetrahydrofuran, and PTMG1000 is polytetrahydrofuran-1000, purchased from German BASF.
Preferably, described urethane resin is polymerized by Isocyanate prepolymers body and B component, wherein,
B component:
The polyvalent alcohol of 80-100 weight part;
The chainextender of 0-10 weight part;
The catalyzer of 0.1-1 weight part;
The alcohol acid of 0.1-2 weight part;
The inner pattern releasing agent applicable of 1-5 weight part;
The water-removal agent of 1-5 weight part;
The filler of 0-10 weight part;
Wherein, Isocyanate prepolymers body and B component weight ratio are 100: 100 to 200: 100.
Preferably, described polyvalent alcohol is polyether glycol or polyester polyol, and the functionality of described polyether glycol or polyester polyol is 2,3,4 or 8, and hydroxyl value is 24-800mgKOH/g.
Preferably, described chainextender is one or more in BDO, glycerol, glycol ether, ethylene glycol, quadrol and tetramethylolmethane.
Preferably, described catalyzer is by amine catalyst, and at least one organo-metallic tin, organo-metallic mercury, organo-metallic bismuth and organo-metallic are plumbous compositely obtains.
Preferably, the hydroxy functional group of described alcohol acid is 1-2, and carboxyl functional group is 1.
Preferably, described inner pattern releasing agent applicable is one or more in stearic acid, paraffin powder and polyether silicone oil.
Preferably, described water-removal agent is one or more in triethyl orthoformate, calcium oxide, lagoriolite, oxazolidine and molecular sieve.
Preferably, described filler is one or more in calcium carbonate, aluminium hydroxide, talcum powder, kaolin and titanium dioxide.
In any one technical scheme above-mentioned, described fortifying fibre can be general fortifying fibre, is specifically as follows glass fibre, carbon fiber, aramid fiber, polypropylene, nylon, basalt fibre etc.
The invention still further relates to the preparation method of the matrix material of above-mentioned pultrusion polyurethane resin, comprise the following steps:
Be that aliphatic isocyanates and the weight fraction of 60%-100% is the mechanical strength of the improved aliphatic polyurethane of 0%-40% and has and can form Isocyanate prepolymers body with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester by weight fraction;
The polymerization of Isocyanate prepolymers body is formed the matrix material of pultrusion polyurethane resin.
Preferably, the described matrix material polymerization of Isocyanate prepolymers body being formed pultrusion polyurethane resin, comprising:
Isocyanate prepolymers body is placed in glue-injection machine A barrel;
The filler of the inner pattern releasing agent applicable of the alcohol acid of the catalyzer of the chainextender of the polyvalent alcohol of 80-100 weight part, 0-10 weight part, 0.1-1 weight part, 0.1-2 weight part, 1-5 weight part, the water-removal agent of 1-5 weight part and 0-10 weight part is placed in glue-injection machine B barrel, and mixes;
By the component in the component in A barrel and B barrel with 100: 100-200: 100 weight ratio inject glue-injection box through glue-injection machine mixing, fortifying fibre to be infiltrated, and by its pultrusion.
In technical solution of the present invention, first in A barrel, load black material, i.e. Isocyanate prepolymers body, then in B barrel, white material is loaded, the i.e. polyvalent alcohol of 80-100 weight part, the chainextender of 0-10 weight part, the catalyzer of 0.1-1 weight part, the alcohol acid of 0.1-2 weight part, the inner pattern releasing agent applicable of 1-5 weight part, the water-removal agent of 1-5 weight part and the filler of 0-10 weight part, then by a certain percentage the component in the component in A barrel and B barrel and fortifying fibre are infiltrated, last pultrusion obtains the matrix material of pultrusion polyurethane resin of the present invention, wherein, also can first feed to B barrel, again A barrel is feeded, also can feed respectively to A barrel and B barrel simultaneously, the present invention does not limit this.
The matrix material of pultrusion polyurethane resin prepared by the present invention may be used for manufacturing solar bracket, electric pole, sash and cable bearer, extends its work-ing life.
Embodiment
In order to the technical problem that the matrix material resistance of oxidation solving pultrusion polyurethane resin in prior art is poor, the invention provides matrix material of a kind of pultrusion urethane and preparation method thereof.In this technical scheme, aliphatic isocyanates is used to instead of existing aromatic isocyanate, and add and high performancely improve the mechanical strength of aliphatic polyurethane and have and can define performed polymer with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester, because aliphatic isocyanic ester not easily photoxidation occurs, therefore extend its in the wild with outdoor application time work-ing life.For making the object, technical solutions and advantages of the present invention clearly, by the following examples the present invention is described in further detail.
First the present invention provides a kind of matrix material of pultrusion polyurethane resin, and comprise fortifying fibre and urethane resin that weight ratio is 75-90: 10-25, wherein, described urethane resin is polymerized by Isocyanate prepolymers body, wherein:
Based on the gross weight of described Isocyanate prepolymers body, it is that the aliphatic isocyanates of 60%-100% and weight fraction are the mechanical strength of the improved aliphatic polyurethane of 0%-40% and have the performed polymer that can be formed with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester that described Isocyanate prepolymers body comprises by weight fraction.
In technical solution of the present invention, aliphatic isocyanates is used to instead of existing aromatic isocyanate, and add high performance improve aliphatic polyurethane mechanical strength and to have (to be such as polytetrahydrofuran (PTMG) with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester, polytetrahydrofuran polycaprolactone block polymer (7201A) or poly-hexanodioic acid fourth diester dibasic alcohol) define performed polymer, because aliphatic isocyanic ester not easily photoxidation occurs, therefore extend its in the wild with outdoor application time work-ing life, in addition, PTMG in performed polymer, 7201A or poly-hexanodioic acid fourth diester dibasic alcohol can improve the strength and toughness of aliphatic polyurethane, therefore compensate for the defect of intensity not as aromatic urethane of aliphatic urethane.In addition, by a certain amount of PTMG and 7201A or poly-hexanodioic acid fourth diester dibasic alcohol, with aliphatic isocyanates pre-polymerization, to improve in pultrusion process under normal temperature the wetting capacity of fortifying fibre.
Wherein, urethane resin is polymerized by Isocyanate prepolymers body, and particularly urethane resin is polymerized by pultrusion by Isocyanate prepolymers body.
It is that the aliphatic isocyanates of 60%-100% and weight fraction are the mechanical strength of the improved aliphatic polyurethane of 0%-40% and have the performed polymer that can be formed with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester that described Isocyanate prepolymers body comprises by weight fraction, such as, in Isocyanate prepolymers body, aliphatic isocyanates accounts for the weight fraction of Isocyanate prepolymers body is 60%, 70%, 80%, 90% or 100%, correspondingly, the weight fraction that described primary hydroxyl polyethers or primary hydroxyl polyester account for Isocyanate prepolymers body is 40%, 30%, 20%, 10% or 0.
Primary hydroxyl polyethers is polytetrahydrofuran, PTMG-1000, PTMG-2000 mainly, and main chain is four regular methylene radical and the repeated arrangement (-O-CH of a Sauerstoffatom
2-CH
2-CH
2-CH
2-), do not have side base, molecular chain is regular, and molecular flexibility is good, and water tolerance ability is high, its be polymerized with urethane after can in molecular chain partial crystallization, thus improve mechanical strength.Primary hydroxyl polyester is mainly polymerized by diprotic acid and dibasic alcohol or is obtained by caprolactone open loop, such as primary hydroxyl polyester is polyester diol, conventional polyester diol comprises poly-hexanodioic acid hexylene glycol dibasic alcohol, polybutyleneadipate dibasic alcohol, poly-adipate glycol dibasic alcohol, polycaprolactone, containing the ester functional groups that bond energy is higher in polyester diol, cohesive strength is high, make its polyurethane product mechanical property higher, resistance toheat is better.And polytetrahydrofuran-caprolactone segmented copolymer has the above two advantage concurrently, performance is better.
Have can with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester, namely primary hydroxyl polyethers (or primary hydroxyl polyester) end group can with isocyanate reaction, preferably can with isocyanic ester highly effective reaction, can be such as polytetrahydrofuran, polytetrahydrofuran polycaprolactone block polymer, poly-hexanodioic acid fourth diester dibasic alcohol, wherein, the molecular weight of polytetrahydrofuran can be 500-2000, the molecular weight of polytetrahydrofuran polycaprolactone block polymer can be 1000-2000, and the molecular weight of poly-hexanodioic acid fourth diester dibasic alcohol can be 1000-2000.Aliphatic isocyanates has multiple, for conventional aliphatic isocyanates, can be preferably isophorone diisocyanate and hexamethylene diisocyanate.
Preferably, described Isocyanate prepolymers body is the performed polymer that IPDI and PTMG1000 is formed, performed polymer, the performed polymer of IPDI and PBA1000 formation, the performed polymer of HDI and 7201A formation, the performed polymer of HDI and PBA1000 formation that IPDI and 7201A is formed, wherein, the functionality of described aliphatic isocyanates is 2, NCO% is 5%-30%.The NCO% of such as aliphatic isocyanates is 5%, 10%, 20% or 30%.Can use with reference to specific requirement collocation when embody rule technical scheme of the present invention, in technical solution of the present invention, also a small amount of aromatic isocyanate can be mixed, aromatic isocyanate is such as MDI (diphenylmethanediisocyanate), TDI (tolylene diisocyanate) and NDI (naphthalene diisocyanate), wherein MDI comprises polymeric MDI, pure MDI, by weight percentage, mixed ratio is 0%-60%.Because the cost of aliphatic isocyanates is higher, after the lower-cost aromatic isocyanate that adulterates, can reduce costs.
Preferably, described urethane resin is polymerized by Isocyanate prepolymers body and B component, wherein,
B component:
The polyvalent alcohol of 80-100 weight part;
The chainextender of 0-10 weight part;
The catalyzer of 0.1-1 weight part;
The alcohol acid of 0.1-2 weight part;
The inner pattern releasing agent applicable of 1-5 weight part;
The water-removal agent of 1-5 weight part;
The filler of 0-10 weight part;
Wherein, Isocyanate prepolymers body and B component weight ratio are 100: 100 to 200: 100.
Wherein, urethane resin is polymerized by Isocyanate prepolymers body and B component, and particularly urethane resin is polymerized by pultrusion by Isocyanate prepolymers body and B component.
Preferably, described polyvalent alcohol is polyether glycol or polyester polyol, and the functionality of described polyether glycol or polyester polyol is 2,3,4 or 8, and hydroxyl value is 24-800mgKOH/g.Such as, the hydroxyl value of polyether glycol or polyester polyol is 24mgKOH/g, 40mgKOH/g, 80mgKOH/g, 100mgKOH/g, 300mgKOH/g, 500mgKOH/g or 800mgKOH/g.Such as, for Zibo moral, polyether glycol can believe that the commodity that federal Chemical Co., Ltd. produces are called DMN-600, its hydroxyl value is 600, and functionality is 3, i.e. three official's polyether glycols; Can also believe that the commodity that federal Chemical Co., Ltd. produces are called DMN-450 for Zibo moral, its hydroxyl value is 450, and functionality is 4, i.e. four official's polyether glycols; The commodity can also produced for Zhong Hua international corporation 200 polyethers by name, its hydroxyl value is 56, and functionality is 2, i.e. two official's polyether glycols.These three kinds of polyether glycols can singlely use, and also can combinationally use, and when three combinationally uses, by weight, the weight part of DMN-600, DMN-450 and 220 polyethers is respectively 30-60 part, 20-50 part and 5-10 part.
Preferably, described chainextender is one or more in BDO, glycerol, glycol ether, ethylene glycol, quadrol and tetramethylolmethane.Such as, chainextender is only BDO, or is only glycerol, or be two or more combination of above-claimed cpd, such as, when BDO and glycerol combinationally use, by weight, the weight part of glycerol is 5-10 part, and the weight part of BDO is 5-15 part.Following " one or more " be also representative be only a kind of or two kinds, or more plant.
Preferably, described catalyzer is by amine catalyst, and at least one organo-metallic tin, organo-metallic mercury, organo-metallic bismuth and organo-metallic are plumbous compositely obtains.Wherein amine catalyst is the catalyzer that this area is commonly used, and preferably has the amine catalyst of carryover effects.Such as, amine catalyst is selected from the DabcoW7 (triethylenediamine formate) of purchased from American gas chemical company and the PolycatSA11 (8-diazabicylo 11 carbon-7-alkene (DBU)-phenolate) of purchased from American gas chemical company.Such as, organometallic catalysts is selected from purchased from American and steps the UL-29 (organo-metallic tin class catalyzer) of figure chemical industry, Bicat8 (organo-bismuth and organic zinc class mixed catalyst), the Bicatz (organic zinc class catalyzer) of the leading chemical company of purchased from American of the leading chemical company of purchased from American and the DacboT-12 (organic tin catalyzer) of purchased from American gas chemical company.
Preferably, the hydroxy functional group of described alcohol acid (or being called hydroxycarboxylic acid) is 1-2, and carboxyl functional group is 1.This alcohol acid is such as lactic acid, can extend the gel time under normal temperature.
Preferably, described inner pattern releasing agent applicable is one or more in stearic acid, paraffin powder and polyether silicone oil.Such as, inner pattern releasing agent applicable is purchased from Q2-5186, the INT-1681 of AXEL Technology S. R. L. of the U.S. of Dow Corning Corporation, the INT-1948MCH of AXEL Technology S. R. L. of the U.S. and commercially available paraffin powder.
Preferably, described water-removal agent is one or more in triethyl orthoformate, calcium oxide, lagoriolite, oxazolidine and molecular sieve.
Preferably, described filler is anti-oxidant filler, such as, be one or more in calcium carbonate, aluminium hydroxide, talcum powder, kaolin and titanium dioxide.Wherein titanium dioxide is preferably nano titanium oxide.
In any one technical scheme above-mentioned, described fortifying fibre can be general fortifying fibre, is specifically as follows glass fibre, carbon fiber, aramid fiber, polypropylene, nylon, basalt fibre etc.
In the present invention, all technical characteristics in above-mentioned all technical schemes can arbitrary combination under not conflicting condition, to form the matrix material of pultrusion polyurethane resin of the present invention.
The invention still further relates to the preparation method of the matrix material of above-mentioned pultrusion polyurethane resin, comprise the following steps:
Be that aliphatic isocyanates and the weight fraction of 60%-100% is the mechanical strength of the improved aliphatic polyurethane of 0%-40% and has and can form Isocyanate prepolymers body with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester by weight fraction;
The polymerization of Isocyanate prepolymers body is formed the matrix material of pultrusion polyurethane resin.
Preferably, the described matrix material polymerization of Isocyanate prepolymers body being formed pultrusion polyurethane resin, comprising:
Isocyanate prepolymers body is placed in glue-injection machine A barrel;
The filler of the inner pattern releasing agent applicable of the alcohol acid of the catalyzer of the chainextender of the polyvalent alcohol of 80-100 weight part, 0-10 weight part, 0.1-1 weight part, 0.1-2 weight part, 1-5 weight part, the water-removal agent of 1-5 weight part and 0-10 weight part is placed in glue-injection machine B barrel, and mixes;
By the component in the component in A barrel and B barrel with 100: 100-200: 100 weight ratio inject glue-injection box through glue-injection machine mixing, fortifying fibre to be infiltrated, and by its pultrusion.
In technical solution of the present invention, first in A barrel, load black material, i.e. Isocyanate prepolymers body, then in B barrel, white material is loaded, the i.e. polyvalent alcohol of 80-100 weight part, the chainextender of 0-10 weight part, the catalyzer of 0.1-1 weight part, the alcohol acid of 0.1-2 weight part, the inner pattern releasing agent applicable of 1-5 weight part, the water-removal agent of 1-5 weight part and the filler of 0-10 weight part, then by a certain percentage the component in the component in A barrel and B barrel and fortifying fibre are infiltrated, last pultrusion obtains the matrix material of pultrusion polyurethane resin of the present invention, wherein, also can first feed to B barrel, again A barrel is feeded, also can feed respectively to A barrel and B barrel simultaneously, the present invention does not limit this.Wherein, the processing parameter of this pultrusion is two district's temperature (mould middle-end 15-20 centimetre) 150 DEG C-170 DEG C, three district's temperature (die temperature 180 DEG C-190 DEG C), pultrusion speed be per minute 2-4 rice.
Below enumerate matrix material that pultrusion polyurethane resin of the present invention is preferred embodiment described and preparation method thereof, but the present invention is not limited to following embodiment.In the following embodiments, " part " is " weight part ".The material that each material used in embodiment adopts manufacturer above to produce.
Embodiment 1
Performed polymer (the PTMG1000 that black material: IPDI and PTMG1000 is formed, 60 DEG C are converted into liquid, 110 DEG C of high-temperature pressure-reduction dehydrations, be cooled to 60 DEG C, add IPDI, keep 75 DEG C to stir 80 minutes), wherein IPDI and PTMG1000 weight ratio is 110: 20, NCO% is about 30%, and black material is placed in A barrel.White material: DMN-60050 part, DMN-45048 part, glycerol 2 parts, after high temperature 110 DEG C of decompression dehydration cooling process, add catalyzer UL-290.3 part, Bicat-80.05 part, Bicatz0.1 part, lactic acid 1 part (low temperature 50 DEG C of processed), 2 parts, molecular sieve, inner pattern releasing agent applicable Q2-51862 part, 0.5 part, paraffin powder, nano titanium oxide 1.5 parts, nano-calcium carbonate 3.5 parts, will expect in vain be placed in B barrel and mix.Be that the ratio of 150: 100 is through glue-injection machine mixing injection glue-injection box with weight ratio by the component in the component in A barrel and B barrel, and sized glass fibres, wherein the content of glass fibre in matrix material batten is 81%, and with the speed pultrusion of per minute 2 meters, obtained sample 1.
Embodiment 2
(7201A60 DEG C is converted into liquid to the performed polymer that black material: IPDI and 7201A is formed, 110 DEG C of step-down dehydrations, be cooled to 75 DEG C, add IPDI, keep 75 DEG C of stirring reactions 2 hours), wherein the weight ratio of IPDI and 7201A is 110: 40, NCO% is about 26%, and black material is placed in A barrel.White material: DMN-60050 part, DMN-45048 part, glycerol 2 parts, after high temperature 110 DEG C of decompression dehydration cooling process, add catalyzer UL-290.5 part, Bicat-80.05 part, Bicatz0.1 part, lactic acid 1 part (low temperature 50 DEG C of processed), 2 parts, molecular sieve, inner pattern releasing agent applicable INT-1948MCH3 part, 0.5 part, paraffin powder, nano titanium oxide 1.5 parts, nano-calcium carbonate 3.5 parts, will expect in vain be placed in B barrel and mix.Be that the ratio of 170: 100 is through glue-injection machine mixing injection glue-injection box with weight ratio by the component in the component in A barrel and B barrel, and sized glass fibres, wherein the content of glass fibre in matrix material batten is 81%, and with the speed pultrusion of per minute 2 meters, obtained sample 2.
Embodiment 3
(PBA110 DEG C of decompression dehydration, is cooled to 75 DEG C, adds IPDI the performed polymer that black material: IPDI and PBA1000 is formed, keep 75 DEG C, stirring reaction 2 hours), wherein the weight ratio of IPDI and PBA1000 is 110: 20, NCO% is about 30%, and black material is placed in A barrel.White material: polyethers DMN60050 part, DMN45048 part, glycerol 2 parts, after high temperature 110 DEG C of decompression dehydration process, add except Shui Ji oxazolidine 1 part, lactic acid (low temperature 50 DEG C of processed) 1 part, PolycatS11A10.7 part, Bicat-80.05 part, Bicatz0.1 part, inner pattern releasing agent applicable INT-16812 part, 0.5 part, paraffin powder, nano titanium oxide 1.5 parts, nano-calcium carbonate 3.5 parts, will expect in vain be placed in B barrel and mix.Be that the ratio of 150: 100 is through glue-injection machine mixing injection glue-injection box with weight ratio by the component in the component in A barrel and B barrel, and sized glass fibres, wherein the content of glass fibre in matrix material batten is 81%, and with the speed pultrusion of per minute 2 meters, obtained sample 3.
Embodiment 4
(7201A60 DEG C is converted into liquid to the performed polymer that black material: HDI and 7201A is formed, 110 DEG C of step-down dehydrations, be cooled to 65 DEG C, add HDI, keep 65 DEG C of stirring reactions 2 hours), wherein the weight ratio of HDI and 7201A is 110: 60, NCO% is about 30%, and black material is placed in A barrel.White material: polyethers DMN60050 part, DMN45048 part, glycerol 2 parts, after high temperature 110 DEG C of decompression dehydration process, add except Shui Ji oxazolidine 1 part, lactic acid (low temperature 50 DEG C of processed) 1 part, PolycatSA10.7 part, Bicat-80.05 part, Bicatz0.1 part, inner pattern releasing agent applicable INT-16812 part, 0.5 part, paraffin powder, nano titanium oxide 1.5 parts, nano-calcium carbonate 3.5 parts, will expect in vain be placed in B barrel and mix.Be that the ratio of 150: 100 is through glue-injection machine mixing injection glue-injection box with weight ratio by the component in the component in A barrel and B barrel, and sized glass fibres, wherein the content of glass fibre in matrix material batten is 81%, and with the speed pultrusion of per minute 2 meters, obtained sample 4.
Embodiment 5
Black material: IPDI, is placed in glue-injection machine A barrel.White material: polyethers DMN60050 part, DMN45030 part, Polyether 220 15 parts, glycerol 5 parts, after high-temperature pressure-reduction processed, add except Shui Ji oxazolidine 1 part, lactic acid (low temperature dewatering process) 1 part, PolycatSA10.5 part, Bicat-80.05 part, Bicatz0.1 part, inner pattern releasing agent applicable INT-16812 part, 0.5 part, paraffin powder, nano titanium oxide 1.5 parts, nano-calcium carbonate 3.5 parts, will expect in vain be placed in B barrel and mix.Be that the ratio of 160: 100 is through glue-injection machine mixing injection glue-injection box with weight ratio by the component in the component in A barrel and B barrel, and sized glass fibres, wherein the content of glass fibre in matrix material batten is 81%, and with the speed pultrusion of per minute 2 meters, obtained sample 5.
Embodiment 6
Black material: HDI, is placed in glue-injection machine A barrel.White material: polyethers DMN60050 part, DMN45030 part, Polyether 220 15 parts, glycerol 5 parts, after high-temperature pressure-reduction processed, add except Shui Ji oxazolidine 1 part, lactic acid (low temperature dewatering process) 1 part, PolycatSA10.5 part, Bicat-80.05 part, Bicatz0.1 part, inner pattern releasing agent applicable INT-16812 part, 0.5 part, paraffin powder, nano titanium oxide 1.5 parts, nano-calcium carbonate 3.5 parts, will expect in vain be placed in B barrel and mix.Be that the ratio of 220: 100 is through glue-injection machine mixing injection glue-injection box with weight ratio by the component in the component in A barrel and B barrel, and sized glass fibres, wherein the content of glass fibre in matrix material batten is 81%, and with the speed pultrusion of per minute 2 meters, obtained sample 6.
Comparative example 1
Black material: polymeric MDI, is placed in glue-injection machine A barrel.White material: polyethers DMN60050 part, DMN45030 part, Polyether 220 15 parts, glycerol 5 parts, after high-temperature pressure-reduction processed, add except Shui Ji oxazolidine 1 part, lactic acid (low temperature 50 DEG C of processed) 1 part, PolycatSA10.5 part, Bicat-80.05 part, Bicatz0.1 part, inner pattern releasing agent applicable INT-16812 part, 0.5 part, paraffin powder, nano titanium oxide 1.5 parts, nano-calcium carbonate 3.5 parts, will expect in vain be placed in B barrel and mix.Be that the ratio of 140: 100 is through glue-injection machine mixing injection glue-injection box with weight ratio by the component in the component in A barrel and B barrel, and sized glass fibres, wherein the content of glass fibre in matrix material batten is 81%, and with the speed pultrusion of per minute 2 meters, obtained control sample 1.
According to standard, mechanical test (GB/T1499, GB/T1447) and ultraviolet light and aging experiment (GB/T14522) are done respectively to above-mentioned sample and control sample.Result is as shown in table 1.
Table 1
From the data in table 1, as control sample 1, the mechanical property of aromatic urethane matrix material is better, but in the wild under illumination condition, aging speed is faster, and time limit of service is shorter.And as sample 1 to sample 6, aliphatic polyurethane matrix material through the polyether-modified back draft intensity of high-performance polyester slightly lower than aromatic urethane, but its toughness outstanding (flexural strength), the ability that ultraviolet resistance is aging outclass aromatic series, and time limit of service is 2-3 times of aromatic urethane.Wherein in aliphatic polyurethane, the mechanical property of IPDI class is better, and the weather resistance of HDI class is better.
Obviously, those skilled in the art can carry out various change and modification to the present invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. a matrix material for pultrusion polyurethane resin, is characterized in that, comprise fortifying fibre and urethane resin that weight ratio is 75-90: 10-25, wherein, described urethane resin is polymerized by Isocyanate prepolymers body, wherein:
Based on the gross weight of described Isocyanate prepolymers body, it is that the aliphatic isocyanates of 60%-100% and weight fraction are the mechanical strength of the improved aliphatic polyurethane of 0%-40% and have the performed polymer that can be formed with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester that described Isocyanate prepolymers body comprises by weight fraction.
2. the matrix material of pultrusion polyurethane resin as claimed in claim 1, it is characterized in that, describedly improve the mechanical strength of aliphatic polyurethane and have and can be selected from polytetrahydrofuran, polytetrahydrofuran polycaprolactone block polymer and polyester diol with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester, and/or
Described aliphatic isocyanates is selected from isophorone diisocyanate and hexamethylene diisocyanate.
3. the matrix material of pultrusion polyurethane resin as claimed in claim 1 or 2, it is characterized in that, described Isocyanate prepolymers body is selected from: the performed polymer that isophorone diisocyanate and polytetrahydrofuran are formed, the performed polymer that isophorone diisocyanate and polytetrahydrofuran polycaprolactone block polymer are formed, the performed polymer that isophorone diisocyanate and polyester diol are formed, the performed polymer that hexamethylene diisocyanate and polytetrahydrofuran polycaprolactone block polymer are formed, the performed polymer that hexamethylene diisocyanate and polyester diol are formed, wherein, the functionality of described aliphatic isocyanates is 2, NCO% is 5%-30%.
4. the matrix material of the pultrusion polyurethane resin as described in any one of claim 1-3, is characterized in that, described urethane resin is polymerized by Isocyanate prepolymers body and B component, wherein,
B component:
The polyvalent alcohol of 80-100 weight part;
The chainextender of 0-10 weight part;
The catalyzer of 0.1-1 weight part;
The alcohol acid of 0.1-2 weight part;
The inner pattern releasing agent applicable of 1-5 weight part;
The water-removal agent of 1-5 weight part;
The filler of 0-10 weight part;
Wherein, Isocyanate prepolymers body and B component weight ratio are 100: 100 to 200: 100.
5. the matrix material of pultrusion polyurethane resin as claimed in claim 4, it is characterized in that, described polyvalent alcohol is polyether glycol or polyester polyol, and the functionality of described polyether glycol or polyester polyol is 2,3,4 or 8, and hydroxyl value is 24-800mgKOH/g.
6. the matrix material of pultrusion polyurethane resin as claimed in claim 4, is characterized in that, described chainextender is one or more in BDO, glycerol, glycol ether, ethylene glycol, quadrol and tetramethylolmethane.
7. the matrix material of pultrusion polyurethane resin as claimed in claim 4, is characterized in that, described catalyzer is by amine catalyst, and at least one organo-metallic tin, organo-metallic mercury, organo-metallic bismuth and organo-metallic are plumbous compositely obtains.
8. the matrix material of pultrusion polyurethane resin as claimed in claim 4, it is characterized in that, the hydroxy functional group of described alcohol acid is 1-2, and carboxyl functional group is 1.
9. a preparation method for the matrix material of the pultrusion polyurethane resin according to any one of claim 1-8, is characterized in that, comprises the following steps:
Be that aliphatic isocyanates and the weight fraction of 60%-100% is the mechanical strength of the improved aliphatic polyurethane of 0%-40% and has and can form Isocyanate prepolymers body with the primary hydroxyl polyethers of the end group of isocyanate reaction or primary hydroxyl polyester by weight fraction;
The polymerization of Isocyanate prepolymers body is formed the matrix material of pultrusion polyurethane resin.
10. method as claimed in claim 9, the described matrix material polymerization of Isocyanate prepolymers body being formed pultrusion polyurethane resin, comprising:
Isocyanate prepolymers body is placed in glue-injection machine A barrel;
The filler of the inner pattern releasing agent applicable of the alcohol acid of the catalyzer of the chainextender of the polyvalent alcohol of 80-100 weight part, 0-10 weight part, 0.1-1 weight part, 0.1-2 weight part, 1-5 weight part, the water-removal agent of 1-5 weight part and 0-10 weight part is placed in glue-injection machine B barrel, and mixes;
By the component in the component in A barrel and B barrel with 100: 100-200: 100 weight ratio inject glue-injection box through glue-injection machine mixing, fortifying fibre to be infiltrated, and by its pultrusion.
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