CN104829809A - High-molecular foam material - Google Patents

High-molecular foam material Download PDF

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Publication number
CN104829809A
CN104829809A CN201410047342.9A CN201410047342A CN104829809A CN 104829809 A CN104829809 A CN 104829809A CN 201410047342 A CN201410047342 A CN 201410047342A CN 104829809 A CN104829809 A CN 104829809A
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acid
diglycidylether
ester
ether
glycidyl
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王祖文
王祖武
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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
    • C08G18/28—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high-molecular foam material, which includes following raw materials: a double activity terminal group polymer, a compound having two or more isocyanate functional groups, a compound having multiple functional groups, an acid anhydride compound having two or more functional groups, an epoxy compound having two or more functional groups, a double-oxazoline compound, an enhancing agent, a flame retardant, a crystal nucleation agent, an accelerant, a toughening agent, a filling agent and an anti-oxygen agent. A process of preparing the high-molecular foam material includes steps of drying the components respectively, performing extrusion in a screw extruder and shaping or roll-pressing an extruded product.

Description

A kind of high molecular foam material
Technical field
The present invention relates to thermoplastic macromolecule material technical field, particularly relate to a kind of high molecular foam material and preparation method thereof.
Background technology
Generally foaming agent foam is adopted to this kind of thermoplastic material of double activated end group polymer.Whipping agent is divided into pneumatogen and chemical foaming agent.Pneumatogen has: chloro-fluoro-carbon kind, hydro carbons and pressurized gas are (as nitrogen and CO 2).The service requirements of this kind of whipping agent is: its temperature and pressure must ensure that whipping agent mixes with plastics in liquid form.Whipping agent just can be made to vaporize when changing temperature and/or pressure, namely starting foaming.Chemical foaming agent can be divided into two main Types: organic chemicals and inorganic chemical.Organic chemistry whipping agent kind is very many, and inorganic chemical foaming agent is limitednumber then.Chemical foaming agent is the earliest simple inorganic carbonate and supercarbonate.CO can be released after this kind of chemical heating 2, they finally be instead of by the mixed thing of supercarbonate and citric acid, because the outcome of the latter is far better.Current more outstanding inorganic foaming agent, its chemism is substantially same as described above, is that poly-carbonic acid class (Poly-carbonicacids) is mixed with carbonate.The decomposition of poly-carbonic acid is thermo-negative reaction, and at about 320F, every gram of acid can release the CO of about 100cc. 2, when being heated to about 390F further, more gas will be released.The endothermic nature of this decomposition reaction may bring benefit to a certain degree, because the loose heat that removes is a large problem in foaming process.Except the gas source as foaming, this kind of material is also used as the nucleating agent of pneumatogen often.The initial abscess formed when it is believed that this kind of chemical foaming agent decomposes, the gas for pneumatogen releasing subsequently provides the place of migration.
Contrary with inorganic foaming agent, alternative organic chemistry whipping agent is various in style, and physical aspect is also different separately.Past is once evaluated for some years hundreds ofly may be used as the organic chemicals of whipping agent.The criterion being used for passing judgment on is also a lot.Most important several are: at controllable speed and can under the condition of estimating temperature, the gas discharged not only is measured greatly, and reproducibility is good; The gas that reaction produces and solid are nontoxic person, and can not have any detrimentally affect for the polymkeric substance of foaming, such as, produce color or unpleasant odor.
Add moisture temperature very responsive because double activated end group polymer melt viscosity is on the low side, in fact this kind of material can only could realize foaming down under some specific high viscosity trade mark or specified conditions, in order to solve this kind of material, particularly it reclaims foaming technique difficult problem the present invention that waste material and mixing reclaim waste material and Reaction extrusion and reactive foaming is combined together, and foamer is CO 2,nonpoisonous and tasteless harmless, solve this difficult problem well, and achieve the new high molecular foam material with excellent properties.
Summary of the invention
The polyisocyanates that the present invention adopts both can react with residual minor amount of water in double activated end group polymer and discharge CO 2it also avoid the degraded of moisture to the high-temperature material in forcing machine simultaneously, simultaneously isocyanate groups and double activated end group also can be utilized to react thus reach quick chain extension and increase solution intensity, isocyanate groups also can slough CO with the carboxyl reaction in active end group in addition 2, the CO produced in these forcing machine reaction systems 2act as whipping agent, after material is extruded by die head, just obtain foam material of the present invention.
With the addition of polyfunctional compound and two functional groups and above anhydride compound, two functional groups and above epoxy compounds, bisoxazoline compounds in the present invention further to form micro-branched structure improve molecular weight further in reaction system, increase solution intensity to obtain the foam material of high-quality.
Also added intensity and toughness that the components such as toughener, fire retardant, crystallization nucleating agent and promotor, toughner, weighting agent, oxidation inhibitor improve foam material in the present invention, add the characteristics such as flame retardant properties.Further increase the use properties of high molecular foam material of the present invention.
The present invention is not only suitable for double activated end group polymer virgin material, is also suitable for its waste material and materials recycling material simultaneously.
Technical scheme of the present invention is:
A kind of high molecular foam material, composed of the following components by massfraction content:
100 parts of double activated end group polymers
0.1-20 part two functional group and above isocyanic ester
0-5 part polyfunctional compound one or more
One or several in 0-5 part two functional group and above anhydride compound, two functional groups and above epoxy compounds, bisoxazoline compounds
0-100 part toughener
0-100 part fire retardant
0-20 part crystallization nucleating agent and promotor
0-100 part toughner
0-100 part weighting agent
0-5 part oxidation inhibitor.
In said components composition, double activated end group polymer refers to one or more that polymer molecular chain two ends are respectively in the polymkeric substance of hydroxyl or amino or carboxyl, includes but not limited to vibrin (as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), poly terephthalic acid 1.3 propylene glycol ester, PEN (PEN), polyarylester, aliphatic polyester resin etc.), polycarbonate, polymeric amide, poly(lactic acid).Also waste material or materials recycling material that main component is above-mentioned classification is comprised.
In said components composition, two functional groups and above isocyanic ester are comprise one or more in the compound of two and above isocyanate groups in molecular structure.As: 4,4'-diphenylmethanediisocyanate, 4,2'-diphenylmethanediisocyanate, 4,4'-dicyclohexyl methane diisocyanate, 4,2'-dicyclohexyl methane diisocyanate, tolylene diisocyanate, 3-isocyanic ester methylene-3,5,5-trimethylcyclohexylisocyanate, polymethylene multi-phenenyl isocyanate, polymethylene diphenyl diisocyanate.
In above-mentioned composition, polyfunctional compound is have 3 and above active function groups in structure (as hydroxyl, amino, carboxyl) compound in one or more, include but not limited to that polyalcohols is (as glycerine, trimethylolethane, TriMethylolPropane(TMP), trihydroxybutane, butantetraol, tetramethylolmethane, dipentaerythritol, nucite, Xylitol, sorbyl alcohol, N.F,USP MANNITOL, polyvinyl alcohol), polynary acids is (as tartronic acid, dimethylol propionic acid, trimellitic acid, Pyromellitic Acid, glyconic acid, citric acid, naphthalenetetracarbacidic acidic, polyacrylic acid), carbohydrate is (as wood sugar, ribose, glucose, fructose, sucrose, trehalose, maltose), polynary amine (Triethylenetetramine (TETA), tetren, penten, polyethylene polyamine, hexamethylenetetramine), ethylenediamine tetraacetic acid (EDTA), the adjacent phenylacetic acid of quadrol two, Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand-Isosorbide-5-Nitrae, 7,10-tetracarboxylic acid, divinyl pentaacetic acid, aspartic acid, toxilic acid, vinylformic acid, oxysuccinic acid, glycine, oxyacetic acid, iminodiethanoic acid, nitrilotriacetic acid(NTA), α-aminopropionic acid, β-alanine, dipropionic acid, fumaric acid, polyacrylamide, glutamic acid N, N-oxalic acid, diethylene triaminepentaacetic acid(DTPA), ethylenediamine disuccinic acid, methylglycine N, N-oxalic acid, melamine hexa-acetic acid.
In above-mentioned composition, two functional groups and above anhydride compound are one or more in following compound.As Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride ,3,4,9,10-perylene tetracarboxylic acid three acid anhydride, Pyromellitic Acid three acid anhydride, mellitic acid three acid anhydride, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride.
In said components composition, two functional groups and above epoxy compounds are comprise two and with the compound of last epoxide group in molecular structure, as: [(1-methyl ethylidene) is two, and (4,1-ring is sub-for 2,2'- hexyloxygen methylene)] bisoxirane, 3,4-expoxycyclohexyl formic acid-3', 4'-expoxycyclohexyl methyl esters, ethylene glycol diglycidylether, 1,3-PD diglycidylether, 1,3 butylene glycol diglycidylether, BDDE, 1,5-PD diglycidylether, 1,2-neopentyl glycol diglycidyl glyceryl ether, 2,4-neopentyl glycol diglycidyl glyceryl ether, 1,6-hexanediol diglycidyl ether, 1,2-hexanediol diglycidyl ether, 1,5-hexanediol diglycidyl ether, 2,5-hexanediol diglycidyl ether, 2-ethyl-1,3-hexanediol diglycidyl ether, 1,7-heptanediol diglycidylether, 1,2-ethohexadiol diglycidylether, 1,8-ethohexadiol diglycidylether, 1,9-nonanediol diglycidylether, decamethylene-glycol diglycidylether, 1,2-decanediol diglycidylether, 1,12-12 carbon Hexanediol diglycidyl ether, 1,2-12 carbon Hexanediol diglycidyl ether, glycerin diglycidyl ether, TriMethylolPropane(TMP) diglycidylether, 1,1,1-tri-(methylol) ethane diglycidylether, tetramethylolmethane diglycidylether, sorbyl alcohol diglycidylether, neopentylglycol diglycidyl ether, dibromoneopentyl glycol diglycidylether, quinhydrones diglycidylether, benzene xylenol diglycidylether, bisphenol A diglycidyl ether, Hydrogenated Bisphenol A diglycidylether, polyethyleneglycol diglycidylether, ((CH2CH2O) n, n=2 ~ 400), polypropylene glycol diglycidyl ether, ((CH3) CH2CH2O) n, n=2 ~ 100), glycerin triglycidyl ether, two glycerin triglycidyl ethers, tetramethylolmethane triglycidyl ether, sorbyl alcohol triglycidyl ether, glycerol propoxylate thing triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 1,1,1-tri-(methylol) ethane triglycidyl ether, 1,1,1-tri-(hydroxyphenyl) ethane triglycidyl ether, trishydroxymethylnitromethane triglycidyl ether, three (2,3-epoxypropyl) isocyanuric acid ester, fluoro sugar alcohol triglycidyl ether, N, N-diglycidyl-4-glycidyl oxo aniline, the reactant of Epicholorohydrin and the acid of 1,3,5-tri-(2-hydroxyethyl) cyanogen urea, the reactant of Epicholorohydrin and three (methylol) aminomethane, sorbyl alcohol four glycidyl ether, tetramethylolmethane four glycidyl ether, Polyglycerine four glycidyl ether, 4,4-methylene-bis (N, N-diglycidylaniline), silane five glycidyl ether, o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, hexanodioic acid 2-glycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, Diglycidyl Sebacate, triglycidyl isocyanurate, 4,4'-diaminodiphenyl-methane four glycidyl amine, m-xylene diamine four glycidyl amine, 2-glycidyl diglycolamine, N, N(contract-two glyceryls) aniline etc.
In said components composition, bisoxazoline compounds is comprise one or more in the compound of two oxazoline groups in molecular structure, as two oxazoline group benzene, 2, two (2-oxazoline), 2,2-(1,3-penylenes)-bis-(the 2-oxazoline) of 2-.
Described toughener is glass fibre, polyphenylene sulfide fibre, carbon fiber, aluminium nitride whisker, alumina whisker, in silicon carbide whisker, silicon nitride crystal whisker, potassium titanate crystal whisker, calcium sulfate crystal whiskers (anhydrous), magnesiumcarbonate (anhydrous) whisker, aluminium borate whisker, ZnOw, magnesia crystal whisker, calcium sulfate crystal whiskers, calcium carbonate crystal whisker, zirconium dioxide whisker, silicon wafer palpus and one or several after coupling agent treatment of above-mentioned materials.
In above-mentioned composition, fire retardant is one or several in following material or in their coating.These materials are: magnesium hydroxide, magnesiumcarbonate, beryllium carbonate, lead carbonate, magnesium oxide, aluminum oxide, tricresyl phosphate (2, 3-bis-chloropropyl) ester, melamine pyrophosphate, ammonium polyphosphate, encapsulated red phosphorus, pentabromodiphenyl oxide, decabromodiphynly oxide, TDE, two (tribromophenoxy) ethane trimeric cyanamide hydrogen bromide salt, three (dibromo phenyl) phosphoric acid ester, brominated epoxy resin, Brominated Polystyrene, tribromophenol cyanurate, triphenylphosphate, aryl polyphosphonates, triphenylphosphine, triphenylphosphine oxide, trimeric cyanamide, melamine cyanurate, melamine phosphate, nano imvite, layered double-hydroxide, antimonous oxide, poly-thio-phenyl phosphonic acids (9, assorted-10-the phosphono of 10-dihydro-9-oxy is assorted luxuriant and rich with fragrance) penylene ester (PDPTP), tetramethylolmethane, Dyhard RU 100, guanidinesalt and derivative thereof, polymeric pentaerythrityl phosphate, zinc, zinc hydroxyl stannate.
In said components composition, crystallization nucleating agent and promotor are one or several in following material.These materials are: carbon black, graphite, zinc oxide, aluminum oxide, Z 250, aluminium sesquioxide, NazCO 3, NaHCO 3,talcum powder, clay (polynite, hydrotalcite, kaolin, rectorite etc.), pyrophyllite, the Na of M-nitro benzoic acid, K, Ca salt, carboxylic acid lithium/barium/calcium/sodium/potassium/zinc salt, aromatic hydroxyl sulfonate, the Mg of organo phosphorous compounds, Zn salt, Sodium Benzoate derivative, polyester-polyether block copolymer, the an alkali metal salt of polyester oligomer, Wholly aromatic polyester powder, lower molecular weight isotactic PP, high-melting-point PET, ionic polymer (as ethene monomethyl acrylic copolymer sodium salt), liquid crystalline polymers (LCP), tetrafluoroethylene (PTFE), magnesium hydroxide, aluminium hydroxide, basic metal and alkaline-earth sulfate, basic metal and alkaline earth phosphate, basic metal and alkaline-earth silicate, polyoxyethylene glycol, Polyethylene Glycol Bisglycidyl Ether, polyoxyethylene ether or ester, sodium-chlor, barium sulfate, silicon-dioxide, titanium dioxide.
In above-mentioned composition, toughner is one or several in following material.These materials are polypropylene (PP), thermoplastic polyester elastomer (TPEE), ethylene-octene copolymer (POE), acrylic acid-grafted polyethylene, acrylic acid-grafted polypropylene, ethylene-methyl methacrylate glycidyl ester, maleic anhydride graft styrene-butadiene rubber(SBR), maleic anhydride inoculated polypropylene, toxilic acid grafted polyethylene, Thermoplastic Vulcanizate (TPV), acrylonitrile-butadiene-styrene (ABS) plastics (ABS), polystyrene-ethylene-butylene copolymer (SEBS), polyethylene (PE), maleic anhydride-g-SBS, maleic anhydride graft POE, maleic anhydride grafted ABS, glycidyl methacrylate graft polystyrene, glycidyl methacrylate graft POE, glycidyl methacrylate graft ABS, glycidyl methacrylate graft styrene-butadiene rubber(SBR).
In said components composition, weighting agent is one or several in following material.These materials are: carbon black, graphite, zinc oxide, aluminum oxide, Z 250, aluminium sesquioxide, NazCO 3, NaHCO 3, talcum powder, clay (polynite, hydrotalcite, kaolin, rectorite etc.), pyrophyllite, barium sulfate, silicon-dioxide, titanium dioxide, white dyes, tinting material.
In said components composition oxidation inhibitor to be structural formula be in following material one or several.These materials are Irganox1076[Benzenepropanoic acid, 3, 5-bis (1, 1-dimethyl-ethyl)-4-hydroxy-, octadecyl ester], Irganox1010[tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester], two [the 3-(3 of Irganox259[hexylene glycol, 5-di-tert-butyl-hydroxy phenyl) propionic ester]], Irganox 1425[two (3, 5-di-tert-butyl-4-hydroxyl benzyl monoethyl phosphate) calcium salt], IrgafosP-EPQ[4, 4'-[1, 1'-xenyl] subunit di 2 ethylhexyl phosphonic acid-four [2, 4-bis-trimethylphenylmethane base] ester], Irgafos168[tricresyl phosphite (2, 4 di-tert-butyl-phenyl esters)], Irgafos126[two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites], Anox20[tetramethylene (3, 5-bis--tertiary butyl-4-hydroxy phenylpropionic acid) methyl esters], LowinoxGP45 [two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic acid] triethyleneglycol ester], Ultanox626, the Hostanox03[Bis-(3 of Clariant company, 3-bis-(4 '-hydroxy-3 '-tert-butylphenyl) butanoic acid)-glycolester], Hostanox010[Pentaerythryl-tetrakis3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], HostanoxP-EPQ[tetra-(2, 4-di-tert-butyl-phenyl-4, 4 ' xenyl) biphosphinate], HostanoxPAR62, the SumilizerGA-80[3 of Sumitomo Chemical, 9-two [1, 1-dimethyl-2-[(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl]-2, 4, 8, 10-tetra-oxaspiro [5.5] undecane, two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionyloxy]-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxaspiro [5.5] undecanes of 3,9-], SumilizerTP-D[CAS:29598-76-3].
the preparation method of above-mentioned high molecular foam material, comprising:
Step one: take each component and take the temperature adapted to carry out drying and dehydrating by various material behavior, wherein anhydrides, two azoles quinoline class, epoxies, isocyanates material do not need drying treatment.
Step 2: each constituent materials is inserted in high-speed mixer and add extrusion moulding in twin screw extruder hopper after mixing; Or each component materials is metered into extrusion moulding in twin-screw extrusion machine inlet capable respectively simultaneously.
Step 3: the section bar making various foaming after being extruded by die head through the utility appliance that shaping or roll extrusion etc. are different.
embodiment:
Below the specific embodiment of the present invention is illustrated in detail:
Embodiment one:
Get PET 50KG and tetramethylolmethane 100g 140 degree of temperature difference drying 4 hours, add in high speed mixer and add 4,4'-diphenylmethanediisocyanate 1000g again and start shooting after mixing and add screw extrusion press hopper and can obtain PET foam material in the extrusion moulding of 200-270 degree.
Embodiment two:
Get PBT reworked material 50KG, talcum powder 50g respectively 140 degree of temperature dryings 4 hours, add in high speed mixer after adding 4,2'-dicyclohexyl methane diisocyanate 1000g, encapsulated red phosphorus 4000g, short glass fiber 5000g, Irganox1010 10g, Irgafos168 40g, pyromellitic dianhydride 150g start mixing again and add screw extrusion press hopper and can obtain PBT flame-retardant foam material in the extrusion moulding of 200-280 degree.

Claims (14)

1. a high molecular foam material, is characterized in that: described high molecular foam material by 100 parts of double activated end group polymers, add 0.1-20 part two functional group and above isocyanic ester, 0-5 part polyfunctional compound one or more, 0-5 part two functional group and above anhydride compound, two functional groups and above epoxy compounds, in bisoxazoline compounds one or several, 0-100 part toughener, 0-100 part fire retardant, 0-20 part crystallization nucleating agent and promotor, 0-100 part toughner, 0-100 part weighting agent, 0-5 part oxidation inhibitor forms.
2. high molecular foam material as claimed in claim 1, it is characterized in that: described double activated end group polymer refers to one or more that polymer molecular chain two ends are respectively in the polymkeric substance of hydroxyl or amino or carboxyl, include but not limited to vibrin (as PET, PBT, PTT, PEN, polyarylester etc.), polycarbonate, polymeric amide, poly(lactic acid), also comprise waste material or materials recycling material that main component is above-mentioned classification.
3. high molecular foam material as claimed in claim 1, it is characterized in that: described two functional groups and above isocyanic ester are comprise one or more in the compound of two and above isocyanate groups in molecular structure, as: 4, 4'-diphenylmethanediisocyanate, 4, 2'-diphenylmethanediisocyanate, 4, 4'-dicyclohexyl methane diisocyanate, 4, 2'-dicyclohexyl methane diisocyanate, tolylene diisocyanate, 3-isocyanic ester methylene-3, 5, 5-trimethylcyclohexylisocyanate, polymethylene multi-phenenyl isocyanate, polymethylene diphenyl diisocyanate.
4. high molecular foam material as claimed in claim 1, is characterized in that: described polyfunctional compound is have 3 and above active function groups in structure (as hydroxyl, amino, carboxyl, sulfydryl) compound in one or more, include but not limited to that polyalcohols is (as glycerine, trimethylolethane, TriMethylolPropane(TMP), trihydroxybutane, butantetraol, tetramethylolmethane, dipentaerythritol, nucite, Xylitol, sorbyl alcohol, N.F,USP MANNITOL, polyvinyl alcohol), polynary acids is (as tartronic acid, dimethylol propionic acid, trimellitic acid, Pyromellitic Acid, glyconic acid, citric acid, naphthalenetetracarbacidic acidic, polyacrylic acid), carbohydrate is (as wood sugar, ribose, glucose, fructose, sucrose, trehalose, maltose), polynary amine (Triethylenetetramine (TETA), tetren, penten, polyethylene polyamine, hexamethylenetetramine), ethylenediamine tetraacetic acid (EDTA), the adjacent phenylacetic acid of quadrol two, Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand-Isosorbide-5-Nitrae, 7,10-tetracarboxylic acid, divinyl pentaacetic acid, aspartic acid, toxilic acid, vinylformic acid, oxysuccinic acid, glycine, oxyacetic acid, iminodiethanoic acid, nitrilotriacetic acid(NTA), α-aminopropionic acid, β-alanine, dipropionic acid, fumaric acid, polyacrylamide, glutamic acid N, N-oxalic acid, diethylene triaminepentaacetic acid(DTPA), ethylenediamine disuccinic acid, methylglycine N, N-oxalic acid, melamine hexa-acetic acid.
5. high molecular foam material as claimed in claim 1, it is characterized in that: described two functional groups and above anhydride compound are comprise one or more in two or more anhydride group compounds in structure, as Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, naphthalene benzene tetracarboxylic acid acid anhydride.
6. high molecular foam material as claimed in claim 1, it is characterized in that: described two functional groups and above epoxy compounds are the compound comprising two and multiple epoxide group in molecular structure, as: [(1-methyl ethylidene) is two, and (4,1-ring is sub-for 2,2'- hexyloxygen methylene)] bisoxirane, 3,4-expoxycyclohexyl formic acid-3', 4'-expoxycyclohexyl methyl esters, 1,2-cylohexanediol diglycidyl ether, ethylene glycol diglycidylether, two [4-(2,3-glycidoxy) phenyl-propane, ethylene glycol diglycidylether, 1,3-PD diglycidylether, 1,3 butylene glycol diglycidylether, BDDE, 1,5-PD diglycidylether, 1,2-neopentyl glycol diglycidyl glyceryl ether, 2,4-neopentyl glycol diglycidyl glyceryl ether, 1,6-hexanediol diglycidyl ether, 1,2-hexanediol diglycidyl ether, 1,5-hexanediol diglycidyl ether, 2,5-hexanediol diglycidyl ether, 2-ethyl-1,3-hexanediol diglycidyl ether, 1,7-heptanediol diglycidylether, 1,2-ethohexadiol diglycidylether, 1,8-ethohexadiol diglycidylether, 1,9-nonanediol diglycidylether, decamethylene-glycol diglycidylether, 1,2-decanediol diglycidylether, 1,12-12 carbon Hexanediol diglycidyl ether, 1,2-12 carbon Hexanediol diglycidyl ether, glycerin diglycidyl ether, TriMethylolPropane(TMP) diglycidylether, 1,1,1-tri-(methylol) ethane diglycidylether, tetramethylolmethane diglycidylether, sorbyl alcohol diglycidylether, neopentylglycol diglycidyl ether, dibromoneopentyl glycol diglycidylether, quinhydrones diglycidylether, benzene xylenol diglycidylether, bisphenol A diglycidyl ether, Hydrogenated Bisphenol A diglycidylether, polyethyleneglycol diglycidylether, ((CH2CH2O) n, n=2 ~ 400), polypropylene glycol diglycidyl ether, ((CH3) CH2CH2O) n, n=2 ~ 100), glycerin triglycidyl ether, two glycerin triglycidyl ethers, tetramethylolmethane triglycidyl ether, sorbyl alcohol triglycidyl ether, glycerol propoxylate thing triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 1,1,1-tri-(methylol) ethane triglycidyl ether, 1,1,1-tri-(hydroxyphenyl) ethane triglycidyl ether, trishydroxymethylnitromethane triglycidyl ether, three (2,3-epoxypropyl) isocyanuric acid ester, fluoro sugar alcohol triglycidyl ether, N, N-diglycidyl-4-glycidyl oxo aniline, the reactant of Epicholorohydrin and the acid of 1,3,5-tri-(2-hydroxyethyl) cyanogen urea, the reactant of Epicholorohydrin and three (methylol) aminomethane, sorbyl alcohol four glycidyl ether, tetramethylolmethane four glycidyl ether, Polyglycerine four glycidyl ether, 4,4-methylene-bis (N, N-diglycidylaniline), , silane five glycidyl ether, o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, hexanodioic acid 2-glycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, Diglycidyl Sebacate, triglycidyl isocyanurate, 4,4'-diaminodiphenyl-methane four glycidyl amine, m-xylene diamine four glycidyl amine, 2-glycidyl diglycolamine, N, N(contract-two glyceryls) aniline etc.
7. high molecular foam material as claimed in claim 1, it is characterized in that: described bisoxazoline compounds is comprise one or more in the compound of two oxazoline groups in molecular structure, as two oxazoline group benzene, 2,2-two (2-oxazoline), 2,2-(1,3-penylene)-bis-(2-oxazoline).
8. high molecular foam material as claimed in claim 1, it is characterized in that: described toughener is glass fibre, polyphenylene sulfide fibre, carbon fiber, aluminium nitride whisker, alumina whisker, in silicon carbide whisker, silicon nitride crystal whisker, potassium titanate crystal whisker, calcium sulfate crystal whiskers (anhydrous), magnesiumcarbonate (anhydrous) whisker, aluminium borate whisker, ZnOw, magnesia crystal whisker, calcium sulfate crystal whiskers, calcium carbonate crystal whisker, zirconium dioxide whisker, silicon wafer palpus and one or several after coupling agent treatment of above-mentioned materials.
9. high molecular foam material as claimed in claim 1, is characterized in that: described fire retardant is one or several in following material or in their coating, and these materials are: magnesium hydroxide, magnesiumcarbonate, beryllium carbonate, lead carbonate, magnesium oxide, aluminum oxide, tricresyl phosphate (2,3-bis-chloropropyl) ester, melamine pyrophosphate, ammonium polyphosphate, encapsulated red phosphorus, pentabromodiphenyl oxide, decabromodiphynly oxide, TDE, two (tribromophenoxy) ethane trimeric cyanamide hydrogen bromide salt, three (dibromo phenyl) phosphoric acid ester, brominated epoxy resin, Brominated Polystyrene, tribromophenol cyanurate, triphenylphosphate, aryl polyphosphonates, triphenylphosphine, triphenylphosphine oxide, trimeric cyanamide, melamine cyanurate, melamine phosphate, nano imvite, layered double-hydroxide, antimonous oxide, poly-thio-phenyl phosphonic acids (assorted-10-phosphono of 9,10-dihydro-9-oxy is assorted luxuriant and rich with fragrance) penylene ester (PDPTP), tetramethylolmethane, Dyhard RU 100, guanidinesalt and derivative thereof, polymeric pentaerythrityl phosphate, zinc, zinc hydroxyl stannate.
10. high molecular foam material as claimed in claim 1, it is characterized in that: described crystallization nucleating agent and promotor are one or several in following material, and these materials are: carbon black, graphite, zinc oxide, aluminum oxide, Z 250, aluminium sesquioxide, NazCO 3, NaHCO 3,talcum powder, clay (polynite, hydrotalcite, kaolin, rectorite etc.), pyrophyllite, the Na of M-nitro benzoic acid, K, Ca salt, carboxylic acid lithium/barium/calcium/sodium/potassium/zinc salt, aromatic hydroxyl sulfonate, the Mg of organo phosphorous compounds, Zn salt, Sodium Benzoate derivative, polyester-polyether block copolymer, the an alkali metal salt of polyester oligomer, Wholly aromatic polyester powder, lower molecular weight isotactic PP, high-melting-point PET, ionic polymer (as ethene monomethyl acrylic copolymer sodium salt), liquid crystalline polymers (LCP), tetrafluoroethylene (PTFE), magnesium hydroxide, aluminium hydroxide, basic metal and alkaline-earth sulfate, basic metal and alkaline earth phosphate, basic metal and alkaline-earth silicate, polyoxyethylene glycol, Polyethylene Glycol Bisglycidyl Ether, polyoxyethylene ether or ester, sodium-chlor, barium sulfate, silicon-dioxide, titanium dioxide.
11. high molecular foam materials as claimed in claim 1, it is characterized in that: described toughner is one or several in following material, these materials are polypropylene (PP), thermoplastic polyester elastomer (TPEE), ethylene-octene copolymer (POE), acrylic acid-grafted polyethylene, acrylic acid-grafted polypropylene, ethylene-methyl methacrylate glycidyl ester, maleic anhydride graft styrene-butadiene rubber(SBR), maleic anhydride inoculated polypropylene, toxilic acid grafted polyethylene, Thermoplastic Vulcanizate (TPV), acrylonitrile-butadiene-styrene (ABS) plastics (ABS), polystyrene-ethylene-butylene copolymer (SEBS), polyethylene (PE), maleic anhydride-g-SBS, maleic anhydride graft POE, maleic anhydride grafted ABS, glycidyl methacrylate graft polystyrene, glycidyl methacrylate graft POE, glycidyl methacrylate graft ABS, glycidyl methacrylate graft styrene-butadiene rubber(SBR).
12. high molecular foam materials as claimed in claim 1, is characterized in that: described weighting agent is one or several in following material, and these materials are: carbon black, graphite, zinc oxide, aluminum oxide, Z 250, aluminium sesquioxide, NazCO 3, NaHCO 3, talcum powder, clay (polynite, hydrotalcite, kaolin, rectorite etc.), pyrophyllite, barium sulfate, silicon-dioxide, titanium dioxide, white dyes, tinting material.
13. high molecular foam materials as claimed in claim 1, it is characterized in that: described oxidation inhibitor to be structural formula be in following material one or several, these materials are Irganox1076[Benzenepropanoic acid, 3, 5-bis (1, 1-dimethyl-ethyl)-4-hydroxy-, octadecyl ester], Irganox1010[tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester], two [the 3-(3 of Irganox259[hexylene glycol, 5-di-tert-butyl-hydroxy phenyl) propionic ester]], Irganox 1425[two (3, 5-di-tert-butyl-4-hydroxyl benzyl monoethyl phosphate) calcium salt], IrgafosP-EPQ[4, 4'-[1, 1'-xenyl] subunit di 2 ethylhexyl phosphonic acid-four [2, 4-bis-trimethylphenylmethane base] ester], Irgafos168[tricresyl phosphite (2, 4 di-tert-butyl-phenyl esters)], Irgafos126[two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites], Anox20[tetramethylene (3, 5-di-t-butyl-4-hydroxy phenylpropionic acid) methyl esters], LowinoxGP45 [two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic acid] triethyleneglycol ester], Ultanox626, the Hostanox03[Bis-(3 of Clariant company, 3-bis-(4 '-hydroxy-3 '-tert-butylphenyl) butanoic acid)-glycolester], Hostanox010[Pentaerythryl-tetrakis3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], HostanoxP-EPQ[tetra-(2, 4-di-tert-butyl-phenyl-4, 4 ' xenyl) biphosphinate], HostanoxPAR62, the SumilizerGA-80[3 of Sumitomo Chemical, 9-two [1, 1-dimethyl-2-[(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl]-2, 4, 8, 10-tetra-oxaspiro [5.5] undecane, two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionyloxy]-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxaspiro [5.5] undecanes of 3,9-], SumilizerTP-D[CAS:29598-76-3].
The preparation method of the high molecular foam material as described in 14. 1 kinds of claims as arbitrary in claim 1 to 13, is characterized in that, comprising:
Step one: take each component and take the temperature adapted to carry out drying and dehydrating by various material behavior, wherein anhydrides, two azoles quinoline class, epoxies, isocyanates material do not need drying treatment,
Step 2: each constituent materials is inserted in high-speed mixer and add extrusion moulding in twin screw extruder hopper after mixing; Or each component materials is metered into extrusion moulding in twin-screw extrusion machine inlet capable respectively simultaneously,
Step 3: through the various section bars of the different utility appliance producing foamed such as shaping or roll extrusion after being extruded by die head.
CN201410047342.9A 2014-02-11 2014-02-11 High-molecular foam material Pending CN104829809A (en)

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CN109705537A (en) * 2018-12-24 2019-05-03 浙江佑威新材料有限公司 The recoverying and utilizing method of release cloth containing epoxy resin
CN109651775A (en) * 2018-12-25 2019-04-19 南通新帝克单丝科技股份有限公司 A kind of chemical thickening method of reuse polyethylene terephthalate
CN109824861A (en) * 2019-01-18 2019-05-31 华北水利水电大学 A kind of modified fluorinated polyurethane resin of polyphenylene sulfide
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CN111704795A (en) * 2020-08-24 2020-09-25 佛山市惠安家居用品有限公司 Sponge for bullet-proof clothes and preparation method thereof
CN112226072A (en) * 2020-09-27 2021-01-15 金旸（厦门）新材料科技有限公司 Semi-aromatic nylon modified material and preparation method thereof
CN112226072B (en) * 2020-09-27 2022-01-25 金旸（厦门）新材料科技有限公司 Semi-aromatic nylon modified material and preparation method thereof
CN112679688A (en) * 2020-12-28 2021-04-20 上海东大聚氨酯有限公司 Low-heat-release quick-release combined polyether, B1-grade flame-retardant polyurethane block foam derived from combined polyether and preparation method of block foam
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Application publication date: 20150812