CN108373528A - A kind of composite matrix resin - Google Patents

A kind of composite matrix resin Download PDF

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Publication number
CN108373528A
CN108373528A CN201710062209.4A CN201710062209A CN108373528A CN 108373528 A CN108373528 A CN 108373528A CN 201710062209 A CN201710062209 A CN 201710062209A CN 108373528 A CN108373528 A CN 108373528A
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Prior art keywords
matrix resin
isocyanate
isocyanate prepolymers
composite
composite matrix
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不公告发明人
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Individual
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Priority to CN201710062209.4A priority Critical patent/CN108373528A/en
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    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • 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
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    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/795—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of mixtures of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates with aromatic isocyanates or isothiocyanates
    • 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
    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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    • C08L75/06—Polyurethanes from polyesters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Abstract

The present invention discloses a kind of composite matrix resin, Isocyanate prepolymers body is contained in its precursor component, and isocyanate-monomer accounts for the ratio of the Isocyanate prepolymers body total weight less than 1% in the Isocyanate prepolymers body.

Description

A kind of composite matrix resin
Abstract
The present invention discloses a kind of composite matrix resin, Isocyanate prepolymers body, and institute are contained in its precursor component It states isocyanate-monomer in Isocyanate prepolymers body and accounts for the ratio of the Isocyanate prepolymers body total weight less than 1%.
Technical field
The present invention relates to a kind of designs of the precursor component of composite matrix resin, further, it is different to be related to a kind of manufacture The method of cyanate performed polymer further is related to manufacturing the method for composite material with this matrix resin and by this base Composite material made of body resin.
Background technology
Polyurethane resin becomes the composite matrix resin rapidly developed, but current industrial quarters because it has excellent performance The polyurethane resin used usually contains the isocyanate-monomer of higher concentration, and isocyanate-monomer is usually harmful, So it is imperative to reduce isocyanate-monomer content to the greatest extent in composite matrix resin.
Invention content
In view of this, the first aspect of the present invention, it provides a kind of composite matrix resin, it is characterized in that：A) institute The precursor component for stating matrix resin contains Isocyanate prepolymers body；B) isocyanate-monomer in the Isocyanate prepolymers body contains The weight ratio that amount accounts for all Isocyanate prepolymers bodies is less than 1%, it is preferable that is less than 500ppm, is more preferably, less than 100ppm is most preferably less than 50ppm.
The preferable case study on implementation of the present invention, it provides a kind of foregoing composite matrix resin, special Sign is：Isocyanate-monomer in the reacting precursor component of the Isocyanate prepolymers body accounts for all Isocyanate prepolymers bodies Reacting precursor component weight ratio be not less than 10%, it is preferable that be not less than 20%, follow preferably not less than 30%.
Another preferable case study on implementation of the present invention, it provides a kind of foregoing containing Isocyanate prepolymers body Composite matrix resin, it is characterized in that：The isocyanate-monomer is selected from methyl diphenylene diisocyanate（MDI）, toluene Diisocyanate（TDI）, naphthalene diisocyanate（NDI）, isophorone diisocyanate（IPDI）, hexa-methylene diisocyanate Ester（HDI）, benzene dimethylene diisocyanate (XDI), methyl cyclohexyl diisocyanate esterification（HTDI）, two cyclohexyl methane Diisocyanate（HMDI）In one or more combinations, it is preferable that be selected from toluene di-isocyanate(TDI)（TDI）, naphthalene two it is different Cyanate（NDI）, isophorone diisocyanate（IPDI）, hexamethylene diisocyanate（HDI）, two isocyanide of phenylenedimethylidyne Acid esters (XDI), two cyclohexyl methane diisocyanates（HMDI）In one or more combinations, it is highly preferred that be selected from toluene Diisocyanate（TDI）, isophorone diisocyanate（IPDI）, hexamethylene diisocyanate（HDI）, methyl cyclohexyl two Isocyanation esterification（HTDI）, two cyclohexyl methane diisocyanates（HMDI）In one or more combinations, most preferably, choosing From toluene di-isocyanate(TDI)（TDI）, isophorone diisocyanate（IPDI）, hexamethylene diisocyanate（HDI）, two rings Dicyclohexylmethane diisocyanate（HMDI）In one or more combinations.
Another preferable case study on implementation of the present invention, it provides a kind of foregoing containing Isocyanate prepolymers body Composite matrix resin, it is characterized in that：A) the reacting precursor component of the Isocyanate prepolymers body further include dihydric alcohol or Diamine；b）The molecular weight of the dihydric alcohol or diamine is less than 2000, it is preferable that is less than 1000, is more preferably, less than 500。
Another preferable case study on implementation of the present invention, it provides a kind of foregoing containing Isocyanate prepolymers body Composite matrix resin, it is characterized in that：A) the reacting precursor component of the Isocyanate prepolymers body contains hydroxyl or amino Compound；B) compound containing hydroxyl or amino contains double bond simultaneously.
Another preferable case study on implementation of the present invention, it provides a kind of foregoing answering containing Isocyanate prepolymers body Condensation material matrix resin, it is characterized in that：It is described containing hydroxyl or amino and at the same time the compound Weight-average molecular containing double bond Amount is less than 2000, is more preferably, less than 1000, is more preferably, less than 500, is most preferably less than 250.
Another preferable case study on implementation of the present invention, it provides a kind of composite matrix resin, it is characterized in that：It is described Containing hydroxyl or amino and at the same time the compound containing double bond includes hydroxy acid compound.
Another preferable case study on implementation of the present invention, it provides a kind of foregoing containing Isocyanate prepolymers body Composite matrix resin, it is characterized in that：The NCO group contents of the Isocyanate prepolymers body are to account for whole pre-polymerization body weights 0 ~ 3%, it is preferable that for the Isocyanate prepolymers body with hydroxy-end capped, the NCO group contents in performed polymer are 0.
The second aspect of the invention, it provides a kind of method preparing Isocyanate prepolymers body, it is characterized in that：It is described Preparation method comprises the steps of：A) carrying out vacuum distillation to the performed polymer reduces isocyanate-monomer content, it is preferable that institute It further includes the steps that being heated to performed polymer to state vacuum distillation step, it is highly preferred that the heating temperature is boiled for isocyanate-monomer Point adds positive/negative 10 degrees Celsius；B) vacuum distillation tail gas is absorbed with the compound containing hydroxyl or amino, it is preferable that Vacuum distillation tail gas is absorbed with the reacting precursor of the performed polymer.
The preferable case study on implementation of the present invention, it provides a kind of method preparing Isocyanate prepolymers body, feature For：The compound containing hydroxyl or amino absorbs the reactant that the isocyanate-monomer in vacuum distillation tail gas is formed It is used further to react with isocyanates.
Another preferable case study on implementation of the present invention, it provides a kind of composite material preparation process, it is characterized in that, it is described multiple Condensation material preparation process is fiber solidifying using foregoing composite matrix resin dipping and is made, it is preferable that described Composite material preparation process is selected from the group of one or more of moulding process of following composite finished product or semi-finished product It closes：Hand is pasted, and is sprayed, winding, resin transfer moulding, priming by vacuum, pultrusion, and reaction injection pultrusion squeezes out, braiding pultrusion, lamination, Molding, sheet molding compound compacting, tubular molding compound compacting, injection, reaction injection, prepreg molding, autoclave molding, pipe crimping, Centrifugal rotation molds, blowing, slush moulding；It is highly preferred that it is selected from resin transfer moulding, and vacuum auxiliary pouring, pultrusion, reaction injection drawing It squeezes, squeezes out, weave the combination of one or more of pultrusion and prepreg molding.
The third aspect of the present invention, it provides a kind of composite material, it is characterized in that, the composite material contains front institute The matrix formed after the composite resin solidification stated is as continuous phase, it is preferable that it also contains fiber as reinforced phase.
Specific implementation mode
The present invention is embodied case and is all made of raw material, equipment and tool cited by upper table, but is not limited to upper table and enumerates Raw material, equipment and tool, analog or substitute known to technical staff each fall within the scope of the present invention in row.
Case study on implementation one：
Matrix resin component A performed polymer prepares：By matrix resin reacting precursor component B2, that is, BDO in molar ratio 1 under room temperature：2 Ratio is added dropwise in matrix resin reacting precursor component A1 i.e. HDI monomers, is protected under dry nitrogen protection during dropwise addition The lasting stirring to reaction mass is held, mixing speed maintains 500rpm；A NCO is detected after being added dropwise every half an hour to contain Amount, until NCO content starts to be evaporated under reduced pressure reaction mass when being reduced to 28%：Reactor will be evacuated to- 0.05MPa, while being heated to 120 degrees Celsius to reaction mass and keeping the stirring to material, and filled in pressure-reducing cushioning tank Enter BDO, distillation tail gas is passed through in the BDO in surge tank, so that HDI monomers therein is absorbed, the BDO for absorbing HDI can Required performed polymer is prepared to be added dropwise in HDI monomers as reaction mass；When detection is evaporated under reduced pressure HDI monomers in tail gas Concentration be less than 50ppm when, discharging obtain performed polymer, measure performed polymer NCO content be 19%.
Matrix resin prepares：By weight 60：40：6：2 first react matrix resin reacting precursor component B1, matrix resin Precursor component B3 is uniformly mixed with matrix resin reacting precursor component additive 1 and matrix resin reacting precursor component additive 2, Being fitted into the storage vat B of matrix resin reactive precursor component meter mix equipment becomes component B, then by matrix resin component A Performed polymer, which is fitted into the storage vat A of matrix resin reactive precursor component meter mix equipment, becomes component A, adjusts the metering Mixing apparatus makes the weight ratio of component A and component B be 149：100, i.e. the equivalent proportion of NCO group and OH groups is 105：100, together When make the temperature of component A be 35 degrees Celsius, the temperature of component B is 35 degrees Celsius.
Equipment prepares：Fiber impregnation equipment and molding die are flatly joined end to end simultaneously in composite molding equipment Close fastening, makes the internal cavity of the two without step seamlessly transit；Fiber impregnation equipment material is that the resin of P20 steel is injected Box, length are 0.7 meter, and the interior penetrating via formula cavity containing tapered contraction from the inlet to the outlet, cavity inner wall polishes chromium plating, Cavity entrance opening dimension is 220mm wide, 11mm high；The size of cavity outlet is identical as molding die internal cavity size；Syringe case The injection orifice that internal diameter is 8mm is provided in the middle part of cavity；Molding die is that material is P20 steel, and 1.3 meters of length includes wide 120mm, high The parallel penetrating via formula cavity of 1.8mm, cavity inner wall polish chromium plating；Die entrance and outlet both ends are respectively provided with one up and down To coldplate, the heating plate of about three pairs distributions is equipped between entrance and exit successively, by the thermometer hole being inserted on mold Thermocouple monitoring controls mold temperature；The temperature of molding die is controlled as from the inlet to the outlet：20 degrees Celsius/90 is Celsius / 180 degrees Celsius/200 degrees Celsius/80 degrees Celsius of degree；By matrix resin reactive precursor component meter mix equipment and mixer And the injection orifice of fiber impregnation equipment is closely connected by pipeline；With the traction clamping device in composite molding equipment by 79 Bundle fiber is drawn across forward fiber impregnation equipment and molding die in the horizontal direction, and hauling speed is adjusted to 0.1 m/min Clock.
Composite molding：Start matrix resin reactive precursor component meter mix equipment, then each matrix resin Reactive component is measured in the ratio of setting and is pumped to mixer, by mixer after mixing by injection fiber impregnation Equipment, when observing that the entrance of fiber impregnation equipment has the mixture of resin precursor component to emerge starting composite molding sets It is standby, fiber is drawn through forward to fiber impregnation equipment and molding die in the horizontal direction, then before resin matrix reactivity The mixture of body component is impregnated with fiber in fiber impregnation equipment and is solidified into resin matrix in molding die to fine Dimension enhancing composite material flat plate is able to be made and is continuously pulled out molding die；Obtained fibre reinforced composites In long fibre account for whole composite materials weight ratio be 75 ~ 81%, volume ratio be 62 ~ 66%, correspondingly, obtained fiber increase The weight ratio that resin matrix in strong composite material accounts for whole composite materials is 19 ~ 25%, and volume ratio is 34 ~ 38%；Entire production Inspection does not measure HDI monomers in the process；Exposure exposes phenomenon to the open air in 6 months to the composite material of gained without apparent glass fibre outdoors.
Case study on implementation two：
Matrix resin reacting precursor component A1 is substituted with matrix resin reacting precursor component A2, above procedure is repeated, i.e., is first made Matrix resin precursor component A performed polymers, vacuum distillation is until isocyanate-monomer content measures performed polymer NCO less than 50ppm Content is 21%, and absorbing the isocyanate-monomer in distillation tail gas with BDO while vacuum distillation reuses, then by gained To matrix resin precursor component A performed polymers and case study on implementation one in the matrix resin component B that is mixed to get be respectively charged into matrix In storage tank A and B in resin precursor component meter mix equipment, setting ratio makes in NCO group and component B in component A OH groups molar ratio be 105：100, then the repeatedly composite material preparation process process of case study on implementation one, is made fiber Enhance composite material flat plate, TDI monomers are not measured in entire technical process.
Case study on implementation three：
Add 50% matrix resin reacting precursor component A1 with 50% matrix resin reacting precursor component A2, repeats above procedure, i.e., Matrix resin precursor component A performed polymers are first made, vacuum distillation is until isocyanate-monomer content measures pre-polymerization less than 50ppm Body NCO contents are 19.3%, and absorbing the isocyanate-monomer in distillation tail gas with BDO while vacuum distillation reuses, so The matrix resin component B difference that will be mixed to get in obtained matrix resin precursor component A performed polymers and case study on implementation one afterwards Be fitted into the storage tank A and B in matrix resin precursor component meter mix equipment, setting ratio make NCO group in component A with The molar ratio of OH groups in component B is 105：100, the then repeatedly composite material preparation process process of case study on implementation one, Fibre reinforced composites tablet is made, TDI and HDI monomers are not measured in entire technical process；The composite material of gained is at family Outer exposure exposes phenomenon to the open air in 6 months without apparent glass fibre.
Case study on implementation four：
Matrix resin component A performed polymer prepares：By matrix resin reacting precursor component A1, that is, HDI in molar ratio 1 under room temperature：2 Ratio is added dropwise in matrix resin reacting precursor component B4 i.e. HEA monomers, is protected under dry nitrogen protection during dropwise addition The lasting stirring to reaction mass is held, mixing speed maintains 500rpm；A NCO is detected after being added dropwise every half an hour to contain Amount, until NCO content starts to be evaporated under reduced pressure reaction mass when being reduced to 1%：Reactor will be evacuated to- 0.05MPa, while being heated to 100 degrees Celsius to reaction mass and keeping the stirring to material, and filled in pressure-reducing cushioning tank Enter HEA, distillation tail gas is passed through in the HEA in surge tank, so that HDI monomers and HEA monomers therein is absorbed, absorbs The HEA of HDI can be used as reaction mass to be added in HEA monomers and prepare required performed polymer；When detection is evaporated under reduced pressure in tail gas When the concentration of HDI monomers and HEA monomers is less than 50ppm, discharging obtains hydroxy-end capped Isocyanate prepolymers body；In performed polymer The matrix resin component additive 3 that the middle addition performed polymer weight ratio is 1% stirs evenly, and adds the pre-polymerization body weight Than for 0.5% matrix resin component additive 4, stirring evenly to form matrix resin precursor mixture, then with mixed matrix resin Precursor mixture is impregnated with 6 layers of fabric with hand paste technique, cures at 80 degrees celsius, obtains composite material flat plate, outdoors 6 months no glasses of exposure expose phenomenon to the open air.
Although the composite matrix resin of the present invention is illustrated above in association with preferred embodiment, this skill Those of ordinary skill in art field is it should be appreciated that above-mentioned example is intended merely to explanation, and cannot function as to the present invention's Limitation；Therefore, modification can be carried out to the present invention in the spirit of claims；These modifications will all be fallen at this Within the scope of claims of invention are required.

Claims (13)

1. a kind of composite matrix resin, it is characterized in that：A) precursor component of described matrix resin contains Isocyanate prepolymers Body；B) isocyanate-monomer content in the Isocyanate prepolymers body accounts for the weight ratio of all Isocyanate prepolymers bodies Less than 1%.
2. the composite matrix resin described in claim 1, it is characterized in that：The reacting precursor of the Isocyanate prepolymers body The weight ratio that isocyanate-monomer in component accounts for all reacting precursor components of the Isocyanate prepolymers body is not less than 10%。
3. the composite matrix resin described in claim 2, it is characterized in that：The isocyanate-monomer is selected from diphenylmethyl Alkane diisocyanate（MDI）, toluene di-isocyanate(TDI)（TDI）, naphthalene diisocyanate（NDI）, isophorone diisocyanate （IPDI）, hexamethylene diisocyanate（HDI）, benzene dimethylene diisocyanate (XDI), methyl cyclohexyl diisocyanate Esterification（HTDI）, two cyclohexyl methane diisocyanates（HMDI）In one or more combinations.
4. the composite matrix resin described in claim 2 ~ 3, it is characterized in that：A) reaction of the Isocyanate prepolymers body Precursor component further includes dihydric alcohol or diamine；b）The molecular weight of the dihydric alcohol or diamine is less than 2000.
5. the composite matrix resin described in claim 2 ~ 4, it is characterized in that：A) reaction of the Isocyanate prepolymers body Precursor component includes the compound containing hydroxyl or amino；B) compound containing hydroxyl or amino contains double simultaneously Key.
6. the composite matrix resin described in claim 5, it is characterized in that：It is described containing hydroxyl or amino and at the same time Compound weight average molecular weight containing double bond is less than 2000.
7. the composite matrix resin described in claim 5 ~ 6, it is characterized in that：It is described containing hydroxyl or amino and same The compound of Shi Hanyou double bonds includes hydroxy acid compound.
8. the composite matrix resin described in claim 2 ~ 7, it is characterized in that：NCO in the Isocyanate prepolymers body The ratio that group accounts for whole pre-polymerization body weights is 0 ~ 3%.
9. the composite matrix resin described in claim 2 ~ 7, it is characterized in that：NCO in the Isocyanate prepolymers body The ratio that group accounts for whole pre-polymerization body weights is 0 and with hydroxy-end capped.
10. a kind of method preparing Isocyanate prepolymers body, it is characterized in that：The preparation method comprises the steps of：A) to institute It states performed polymer and carries out vacuum distillation reduction isocyanate-monomer content；B) tail gas will be evaporated under reduced pressure with containing hydroxyl or amino Compound is absorbed.
11. the method for preparing Isocyanate prepolymers body described in claim 10, it is characterized in that：It is described containing hydroxyl or ammonia The compound of base absorb vacuum distillation tail gas in isocyanate-monomer formed reactant be used further to it is anti-with isocyanates It answers.
12. a kind of composite material preparation process, it is characterized in that, the composite material preparation process uses institute in claim 1 ~ 9 The composite matrix resin dipping stated is fiber solidifying and is made.
13. a kind of composite material, it is characterized in that, it is solid that the composite material contains the composite resin described in claim 1 ~ 9 The matrix formed after change is as continuous phase.
CN201710062209.4A 2017-02-01 2017-02-01 A kind of composite matrix resin Pending CN108373528A (en)

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