CN108219181A - A kind of degradable poly terephthaldehyde acids expanded material and preparation method thereof - Google Patents
A kind of degradable poly terephthaldehyde acids expanded material and preparation method thereof Download PDFInfo
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- CN108219181A CN108219181A CN201711425424.2A CN201711425424A CN108219181A CN 108219181 A CN108219181 A CN 108219181A CN 201711425424 A CN201711425424 A CN 201711425424A CN 108219181 A CN108219181 A CN 108219181A
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- expanded material
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- 239000000463 material Substances 0.000 title claims abstract description 56
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical class O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005187 foaming Methods 0.000 claims abstract description 46
- 230000015556 catabolic process Effects 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000006731 degradation reaction Methods 0.000 claims abstract description 29
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- 239000004088 foaming agent Substances 0.000 claims abstract description 26
- 239000002667 nucleating agent Substances 0.000 claims abstract description 23
- 239000004970 Chain extender Substances 0.000 claims abstract description 22
- 239000012943 hotmelt Substances 0.000 claims abstract description 21
- 229920003023 plastic Polymers 0.000 claims abstract description 17
- 239000004033 plastic Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- -1 polypropylene terephthalate Polymers 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 25
- 125000005442 diisocyanate group Chemical group 0.000 claims description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 229920003232 aliphatic polyester Polymers 0.000 claims description 12
- 150000003504 terephthalic acids Chemical class 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003022 phthalic acids Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
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- 230000000704 physical effect Effects 0.000 abstract description 7
- 238000012270 DNA recombination Methods 0.000 abstract description 3
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- 150000003503 terephthalic acid derivatives Chemical class 0.000 abstract 2
- 108091028043 Nucleic acid sequence Proteins 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 21
- 239000005058 Isophorone diisocyanate Substances 0.000 description 21
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 21
- 230000001007 puffing effect Effects 0.000 description 14
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 13
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 11
- 239000006260 foam Substances 0.000 description 11
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
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- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- 229920002725 thermoplastic elastomer Polymers 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
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- 239000012948 isocyanate Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 7
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920006389 polyphenyl polymer Polymers 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical compound [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 description 2
- 206010000269 abscess Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229920006237 degradable polymer Polymers 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
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- 230000009477 glass transition Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
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- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IEBJZLRZRKTGFN-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C1=CC=CC=C1 Chemical class N=NC=NN.N=NC=NN.C1=CC=CC=C1 IEBJZLRZRKTGFN-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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Classifications
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- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/022—Foaming unrestricted by cavity walls, e.g. without using moulds or using only internal cores
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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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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- 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
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- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/141—Hydrocarbons
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2203/20—Ternary blends of expanding agents
- C08J2203/202—Ternary blends of expanding agents of physical blowing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The present invention relates to a kind of degradable poly terephthaldehyde acids expanded materials and preparation method thereof, and the expanded material is made of following methods：(1)：Poly terephthalic acid class plastics and degradation agent are put into multiple screw extruder one, shear melting forms the hot melt one with mobility；(2)：Hot melt one is pumped into screw reactor, adds chain extender, is reacted；(3)：Reaction melt is then pumped in multiple screw extruder two, adds crosslinking agent, nucleating agent and foaming agent, mixes homogeneous；(4)：Then, by the output of homogeneous melt pressure and foaming obtained by step (3).Compared with prior art, the present invention carries out processes the such as " → unordered reconstruct of molecule fragment are smashed in macromolecule degradation " by simulating DNA sequence dna recombination, generate supra polymer structure of the main chain containing function fragment and with multi-functional secondary chain, foaming operation time and temperature window etc. are optimized, the physical property enhancing and continuous controllable stablize for realizing poly terephthalic acid class expanded material are foamed.
Description
Technical field
The present invention relates to degradable foam materials field, more particularly, to a kind of degradable poly terephthaldehyde acids foaming material
Material and preparation method thereof.
Background technology
High molecular polymer is widely used in all and human lives relevant every field of the manufacture from aircraft to clothing,
But since most of polymer is from organic hydrocarbon, waste many decades even centuries can not all degrade, and this birdss of the same feather flock together
It closes object and is directly prepared into or is made after foaming the quick consumables such as daily packaging material, cutlery box, easily-consumed products, electron membrane, plastic film for agricultural use.Only
The Chinese non-degradable cutlery box generated every year, nondegradable plastics packaging bag are just up to millions of tons, and service life is average insufficient
20 minutes.The pressure for being difficult to weigh is brought to environment and resource, the whole society all profoundly recognizes from government, enterprise, the common people
To environmental crisis.The exploitation of degradation material at present, the exploitation of material lightweight, higher physical property alternative materials exploitation all into
For most popular research and development field.
The puffing common process route of thermoplastic polymer elastomer at present：Chemical foam blowing agent is blended into, is blended
Enter foamed ball foaming materials, material liquid gas permeability critical in autoclave foams, the critical foaming of screw rod physics.Molding is produced
Technique includes again：Puffing foaming in casting moulds is molded puffing foaming, extrusion molding puffing foaming, foaming furnace foamable etc..Injection hair
The uniform in foaming and expansion ratio of bubble are poor, and the easy melt fracture of material of extruded plastic foam causes abscess breakdown and surface to collapse,
Foaming exists low compared with high safety risk and capacity efficiency in autoclave.It is divided by foam theory：Physical blowing and chemical blowing.No
By any polymer raw material is chosen, no matter also using any foaming method, foaming process will generally pass through：Form gas
The stages such as complex → bubble swelling of nucleus → foam solidifying and setting.
The foaming of degradable thermoplastic polymer elastic material and it is puffing after still need to possess good physical property, this requires
Puffing rear material structure and material abscess etc. are designed.But material structural property itself and processing technology are limited by, is foamed
All various aspects such as the understanding of principle cause the domestic control mode to puffing thermoplastic polymer elastic material simple and unstable
It is fixed, the particularly polymer material of highly crystalline, such as PLA, PET, PBT, PBS, PHA, on material character and processing work
Rarely has stably and controllable puffing case in skill.In addition, existing degradable foam materials are while its degradability is improved, often
Be difficult to ensure that the physical characteristics such as its good tensile strength, although so that expanded material can realize it is degradable, from
Body intensity etc. is not durable not enough, seriously offsets by the original intention that product is related to.The present invention is based on the above problem and proposes.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of degradable polies to benzene
Diformazan acids expanded material and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
It is an object of the present invention to proposing a kind of degradable poly terephthaldehyde acids expanded material, including following heavy
Measure the component of number：0.1-100 parts of poly terephthalic acid class plastics, 0-97 parts of aliphatic polyester, 0-10 parts of degradation agent, chain extender
0.1-10 parts, 0-10 parts of crosslinking agent, 0.01-1 parts of nucleating agent, 0.1-10 parts of foaming agent.
Preferably, the poly terephthalic acid class plastics for PET or PBT or polypropylene terephthalate (PPT or
PTT)。
Preferably, the degradation agent is alcohol, amine or organic dibasic acid.
It is furthermore preferred that the alcohol is short chain glycol, such as butanediol, hexylene glycol or ethylene glycol, described organic two
First acid is binary acid or aromatic dibasic acid.
Preferably, the crosslinking agent uses the compound containing 2 or 2 or more crosslinkable functionalities.It is furthermore preferred that institute
Crosslinking agent is stated using the isocyanates such as diisocyanate, polyisocyanates, nitrogen pyridine etc..Even more preferably, isocyanates
2,4 diisocyanate TDI of toluene, '-diphenylmethane diisocyanate MDI, isophorone diisocyanate IPDI, six can be selected
Methylene diisocyanate HDI, dicyclohexyl methyl hydride diisocyanate HMDI, HDI trimer, polymethylene polyphenyl polyisocyanate cyanogen
One or more of acid esters etc. it is compound.
Preferably, the chain extender uses diisocyanate terminated long-chain Type Polyurethane Prepolymer or both ends by epoxy
The long chain type polymer of base sealing end.It is furthermore preferred that the long-chain Type Polyurethane Prepolymer is 2,4 diisocyanate TDI of toluene, two
The diisocyanate such as phenylmethane diisocyanate MDI, isophorone diisocyanate IPDI or hexamethylene diisocyanate HDI
With the product of polymerization.
Preferably, the nucleating agent is selected from carbon nanotube, talcum powder, nanometer titanium dioxide, modified calcium carbonate, carbon black, stone
At least one of black alkene or tetrafluoroethene pulvis etc..
The foaming agent is selected from CO2、N2, normal butane, at least one of pentane or isopentane etc..
The second object of the present invention is to propose a kind of preparation method of degradable poly terephthaldehyde acids expanded material,
Specifically include following steps：
(1)：0.1-100 parts of poly terephthalic acid class plastics and 0-20 parts of degradation agents are put into multiple screw extruder one,
Shear melting forms the hot melt one with mobility；
(2)：Hot melt one is pumped into screw reactor, adds 0.1-50 parts of chain extenders, is reacted；
(3)：It is then pumped in multiple screw extruder two from the reaction melt of screw reactor outlet discharge, meanwhile, in spiral shell
0-20 parts of crosslinking agents, 0.01-1 portions of nucleating agents and 0.1-10 foaming agents are added in bar extruding machine two, mixes homogeneous；
(4)：Then, by the output of homogeneous melt pressure and foaming obtained by step (3).
Preferably, it is adding in hot melt for the moment in the screw reactor of step (2), is also adding in simultaneously by being no more than 97 parts
Aliphatic polyester hot melt two made of shear melting in multiple screw extruder three.
Preferably, the poly terephthalic acid class plastics for PET or PBT or polypropylene terephthalate (PPT or
PTT)。
Preferably, the degradation agent is alcohol, amine or organic dibasic acid.
It is furthermore preferred that the alcohol is short chain glycol, such as butanediol, hexylene glycol or ethylene glycol, described organic two
First acid is binary acid or aromatic dibasic acid.
Preferably, the crosslinking agent uses the compound containing 2 or 2 or more crosslinkable functionalities.It is furthermore preferred that institute
Crosslinking agent is stated using the isocyanates such as diisocyanate, polyisocyanates, nitrogen pyridine etc..Even more preferably, isocyanates
2,4 diisocyanate TDI of toluene, '-diphenylmethane diisocyanate MDI, isophorone diisocyanate IPDI, six can be selected
Methylene diisocyanate HDI, dicyclohexyl methyl hydride diisocyanate HMDI, HDI trimer, polymethylene polyphenyl polyisocyanate cyanogen
One or more of acid esters etc. it is compound.
Preferably, the chain extender uses diisocyanate terminated long-chain Type Polyurethane Prepolymer or both ends by epoxy
The long chain type polymer of base sealing end.It is furthermore preferred that the long-chain Type Polyurethane Prepolymer is 2,4 diisocyanate TDI of toluene, two
The diisocyanate such as phenylmethane diisocyanate MDI, isophorone diisocyanate IPDI or hexamethylene diisocyanate HDI
With the product of polymerization.
Preferably, the nucleating agent is selected from carbon nanotube, nanometer titanium dioxide, talcum powder, modified calcium carbonate, carbon black, stone
At least one of black alkene or tetrafluoroethene pulvis etc..
The foaming agent is selected from CO2、N2, normal butane, at least one of pentane or isopentane etc..
Preferably, in step (1)：The operation temperature of multiple screw extruder one is 210~250 DEG C；
In step (2)：The operation temperature of screw reactor is 220-260 DEG C.
Preferably, in step (3)：Multiple screw extruder two is divided into leading portion, stage casing and back segment by melt direction of advance, wherein,
The crosslinking agent is added in two leading portion of multiple screw extruder, and nucleating agent adds in two stage casing of multiple screw extruder, and foaming agent is squeezed in screw rod
Two back segment of molding machine adds in；
Melt temperature is controlled in multiple screw extruder two at 200-260 DEG C, melt pressure 70-150bar.
Preferably, foaming includes in step (4)：1. mass expanded foams and shapes in foaming and setting mold, generally
Suitable for crystallization temperature height, the thermoplasticity degradable elastomers for the characteristics such as the fast crystallization of crystallization rate is regular, and molecular weight is big are 2. fixed
To injection molding, the difference of the crystalline rate of material and indefinite kenel leads to partial foaming thermoplastic elastomer (TPE) used by patent
Can puffing shaped piece be made by injection
1. mass expanded foams and shapes in foaming and setting mold, melt passes through melt under the thrust of Bitruder
It pumps under steady pressure and flow rate, then the melt homogeneously containing foaming agent and auxiliary addition agent is passed through into multichannel latus rectum by distributor
Moulding, which is respectively enterd, with runner respectively designs position.When homogeneous melt leaves runner and enters mold, spatial expansion and ambient pressure
Release expands melt side, side filling and cooling.Multichannel latus rectum and the discharging position of runner and latus rectum size, into the position of mold
Putting combine foaming manufactured goods moulding shape and melt temperature, and pressure, glass transition temperature or softening point temperature etc. integrate item
Part designs.Mold is that size and shape according to needed for expanded material manufactured goods are designed and are set with runner and heat tracing and temperature control
Meter.Hot melt is flowed and is filled rapidly in mold, and flux foaming and expansion in flowing and filling, and in temperature controlling instruments
Lower sizing cooling is adjusted, due to the runner of mold, temperature control is vented, and the appearance and size even ring layouts such as mouth of a river are made to control
The final expansion ratio of product, closed air bag and trepanning air passage structure, capillary penetrate through ratio and wall thickness etc. to meet the specific of downstream
Using.
2. vectored injection is molded, the difference of the crystalline rate of material and indefinite kenel leads to partial foaming used by patent
Puffing shaped piece can be made by injection in thermoplastic elastomer (TPE).When the hot melt of high pressure leaves extruding machine end runner, foaming
Agent is propelled during amplifying moment release of pressure in space on melt to profiled piece fixing piece, and melt cools down in foaming and external empty
Between the lower sizing for realizing material of temperature control and expansion ratio matching.
The present invention can additionally incorporate in formula according to actual needs rubber (preferably both ends use hydroxy-end capped rubber),
Lubricant, antioxidant etc..
The present invention is different from preparing for general degradable poly terephthaldehyde acids expanded material in preparation process
It is first, degradation agent to be added by the poly terephthalic acids class plastic section such as PET or PBT by using the multiple screw extruder of high shear
Degradation is divided to be broken into the segment compared with small molecule and is blocked by functional groups such as hydroxyls, then, functional fragment and heat after smashing
Chain extender, the aliphatic polyester of melting (are mainly used to adjust the molding time of subsequent material, to facilitate to obtain more suitable behaviour
Make time window), the unordered reconstruct chain of the simulation DNA regrouping process such as crosslinking agent form the macromolecular with new group and new segment
Segment so that reaction product can have broader operating time and temperature window, is easy to foaming operation, moreover, last
The more secondary chain macromoleculars of polyfunctional group are easier to be expressed in the physical property such as intensity, elasticity, and melting range is also apparent broadening, conducive to product
Following process.In addition, after addition of the cross-linking agent, the part such as PET, aliphatic polyester crosslink reaction be also possible to occur it is similar
The double-spiral structure of DNA, the physical property that such structure is more favorable for final material are promoted.
The polymer molecule regrouping process by simulating DNA recombinations of the present invention, may be such that the foaming operation of these materials
Temperature window is expanded to 5-20 DEG C in the range of 5 DEG C or so, avoids being difficult to practical hair since operation temperature window is too low
The problem of bubble operation, so as to improve expanded material production efficiency and convenience.
Compared with prior art, the present invention has the following advantages：
(1) present invention focuses on the reflow process control of degradable thermoplastic elastomer, degradable polymer molecular structure
Other functional groups are introduced, degradable polymer molecule cross-link is modified, and the melt strength control before flux foaming passes through melt temperature
Degree controls foaming materials multiplying power with pressure and the temperature of release of pressure environment with pressure.Concrete operations are：Pass through Bitruder one
Degradation material is subjected to Partial digestion chain rupture, then again through strand modifying agent, chain extender and crosslinking agent etc. with degradation agent
It introduces new group to carry out repeated order and continue material molecule structure and molecule segment again, so as to obtain specific suitable melt strength and crystallization
Rate so as to the modified degradable polymeric matrix with rational foaming operation time and operation temperature window, and then is realized
The continuous controllable stable foaming of degradable polyalcohol group body.
(2) permeability contrast of the different foaming agents in different polymer materials can be utilized, different materials are not
It is protected in pressure difference with the difference of melt strength caused by melt crystallization speed, the puffing rear physical property variation of different polymer with transitivity
The difference stayed, so as to control it is puffing after material in micro- air bag size and how many and open cells size, shape and it is how many come
The physical property of adjustment material achievees the purpose that meet different downstream uses and customer requirement.
(3) the polymer molecule regrouping process by simulating DNA recombinations of the invention may be such that the foaming behaviour of these materials
Make temperature window and be expanded to 5-20 DEG C in the range of 5 DEG C or so, so as to be conducive to the production operation of foaming.
Description of the drawings
Fig. 1 is the preparation technology flow chart of the present invention.
Specific embodiment
A kind of degradable poly terephthaldehyde acids expanded material includes the component of following parts by weight：Poly- terephthaldehyde
0.1-100 parts of acids plastics, 0-97 parts of aliphatic polyester, 0-10 parts of degradation agent, 0.1-10 parts of chain extender, 0-10 parts of crosslinking agent,
0.01-1 parts of nucleating agent, 0.1-10 parts of foaming agent.
As a kind of preferred embodiment of said program, the poly terephthalic acid class plastics for PET or PBT or
Polypropylene terephthalate (PPT or PTT).
As a kind of preferred embodiment of said program, the degradation agent is alcohol, amine or organic dibasic acid.
It is furthermore preferred that the alcohol is short chain glycol, such as butanediol, hexylene glycol and ethylene glycol, institute can be selected
The organic dibasic acid stated is binary acid or aromatic dibasic acid.
As a kind of preferred embodiment of said program, the aliphatic polyester for adipic acid hexylene glycol ester or oneself
Succinate adipate or adipic acid hexylene glycol butanediol ester.
As a kind of preferred embodiment of said program, the crosslinking agent uses cross-linking containing 2 or 2 or more
The compound of functional group.It is furthermore preferred that the crosslinking agent is using the isocyanates such as diisocyanate, polyisocyanates, nitrogen pyridine
Deng.Even more preferably, isocyanates can select 2,4 diisocyanate TDI of toluene, '-diphenylmethane diisocyanate MDI,
Isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, dicyclohexyl methyl hydride diisocyanate HMDI, HDI tri-
One or more of aggressiveness, poly methylene poly phenyl poly isocyanate etc. it is compound.
As a kind of preferred embodiment of said program, the chain extender uses diisocyanate terminated long-chain
Type Polyurethane Prepolymer or both ends are by long chain type polymer of epoxy radicals end-blocking etc..It is furthermore preferred that the long-chain type polyurethane is pre-
Aggressiveness is 2,4 diisocyanate TDI of toluene, '-diphenylmethane diisocyanate MDI, isophorone diisocyanate IPDI or six sub-
The product of the diisocyanate such as methyl diisocyanate HDI and polymerization.
As a kind of preferred embodiment of said program, the nucleating agent be selected from carbon nanotube, nanometer titanium dioxide,
At least one of talcum powder, modified calcium carbonate, carbon black, graphene or tetrafluoroethene pulvis etc..
As a kind of preferred embodiment of said program, the foaming agent is selected from CO2、N2, normal butane, pentane
Or at least one of isopentane etc..
A kind of preparation method of degradable poly terephthaldehyde acids expanded material, includes the following steps：
(1)：0.1-100 parts of poly terephthalic acid class plastics and 0-10 parts of degradation agents are put into multiple screw extruder one,
Shear melting forms the hot melt one with mobility, at this point, using the high rotating speed cutting of high temperature of screw rod, and coordinate short chain alcohol etc.
The degradation of poly terephthalic acid class parts of plastics is broken into molecule fragment by degradation agent, and causes molecule fragment by functions such as such as hydroxyls
Property group end capping；This step can add in metallic catalyst to promote the progress of degradation reaction, as organic tin/organic zinc/
The catalyst such as organic silver.
(2)：Hot melt one is pumped into screw reactor, it is (diisocyanate terminated to add 0.1-10 parts of chain extenders
Long-chain Type Polyurethane Prepolymer can be 2,4 diisocyanate TDI of toluene, '-diphenylmethane diisocyanate MDI, isophorone
The product of the diisocyanate such as diisocyanate IPDI or hexamethylene diisocyanate HDI and polymerization), reaction, this
Step is mainly using the closed cavity in screw reactor and the screwing element of the heat exchange of energy mixed at high speed, shearing, then urged in metal
Under the action of agent, chain extension is carried out, and form PET's or PBT to there are the macromoleculars of the functional groups such as hydroxyl by chain extender
Such as polyester-type urethano block macromolecule polyalcohol.
(3)：It is then pumped in multiple screw extruder two from the reaction melt of screw reactor outlet discharge, meanwhile, in spiral shell
0-10 parts of crosslinking agents, 0.01-1 portions of nucleating agents and 0.1-10 foaming agents are added in bar extruding machine two, mixes homogeneous, this step is having
Gymnastics can monitor melt viscosity and melt strength in Bitruder two on-line when making, and control melt at 120 DEG C
Open hour (i.e. melt becomes time of crystalline solid from fluid) controlled supervention bubble operation temperature thereafter at 10 seconds or more
There is 5-20 DEG C of section, conducive to being smoothed out for foaming operation, the amount for being mainly adjusted by degradation agent and chain extender is controlled indirectly
Melt strength and viscosity in multiple screw extruder two processed can also add in crosslinking agent and adjust its dosage to be adjusted as needed
The solid additives such as section, crosslinking agent, nucleating agent are thoroughly mixed under the engaged element effect of the region of engagement of twin-screw in melt,
Usual engaged element accounts for the 15~40% of whole spiro rod length, and foaming agent feeds the mixed zone of Bitruder two, and is nibbling
It closes and is uniformly mixed melt and high pressure critical gas under element effect, high pressure gas infiltrates through melt and the quilt centered on nucleating agent
Melt wraps up.
(4)：Then, by the output of homogeneous melt pressure and foaming obtained by step (3).
As a kind of preferred embodiment of said program, the poly terephthalic acid class plastics for PET or PBT or
Polypropylene terephthalate (PPT or PTT).
As a kind of preferred embodiment of said program, the degradation agent is alcohol, amine or organic dibasic acid.
It is furthermore preferred that the alcohol is short chain glycol, such as butanediol, hexylene glycol and ethylene glycol, institute can be selected
The organic dibasic acid stated is binary acid or aromatic dibasic acid.
As a kind of preferred embodiment of said program, the aliphatic polyester for adipic acid hexylene glycol ester or oneself
Succinate adipate or adipic acid hexylene glycol butanediol ester.
As a kind of preferred embodiment of said program, the crosslinking agent uses cross-linking containing 2 or 2 or more
The compound of functional group.It is furthermore preferred that the crosslinking agent is using the isocyanates such as diisocyanate, polyisocyanates, nitrogen pyridine
Deng.Even more preferably, isocyanates can select 2,4 diisocyanate TDI of toluene, '-diphenylmethane diisocyanate MDI,
Isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, dicyclohexyl methyl hydride diisocyanate HMDI, HDI tri-
One or more of aggressiveness, poly methylene poly phenyl poly isocyanate etc. it is compound.
As a kind of preferred embodiment of said program, the chain extender uses diisocyanate terminated long-chain
Type Polyurethane Prepolymer or both ends are by long chain type polymer of epoxy radicals end-blocking etc..It is furthermore preferred that the long-chain type polyurethane is pre-
Aggressiveness is 2,4 diisocyanate TDI of toluene, '-diphenylmethane diisocyanate MDI, isophorone diisocyanate IPDI or six sub-
The product of the diisocyanate such as methyl diisocyanate HDI and polymerization.
As a kind of preferred embodiment of said program, the nucleating agent is selected from carbon nanotube, talcum powder, modification
At least one of calcium carbonate, carbon black, graphene or tetrafluoroethene pulvis etc..
As a kind of preferred embodiment of said program, the foaming agent is selected from CO2、N2, normal butane, pentane
Or at least one of isopentane etc..
As a kind of preferred embodiment of said program, hot melt one is being added in the screw reactor of step (2)
When, it also adds in simultaneously by being no more than 97 parts of the aliphatic polyester hot melt two made of shear melting in multiple screw extruder three.
As a kind of preferred embodiment of said program, in step (1)：The operation temperature of multiple screw extruder one is
210~250 DEG C；
In step (2)：The operation temperature of screw reactor is 220-260 DEG C.
As a kind of preferred embodiment of said program, in step (3)：Multiple screw extruder two presses melt direction of advance
It is divided into leading portion, stage casing and back segment, wherein, the crosslinking agent is added in two leading portion of multiple screw extruder, and nucleating agent is in multiple screw extruder
Two stage casings add in, and foaming agent is added in two back segment of multiple screw extruder；
Melt temperature is controlled in multiple screw extruder two at 200-260 DEG C, melt pressure 70-150bar.
As a kind of preferred embodiment of said program, foaming includes in step (4)：1. foaming and setting mold
Interior mass expanded foams and shapes, and applies in general to crystallization temperature height, the characteristics such as the fast crystallization of crystallization rate is regular, and molecular weight is big
Thermoplasticity degradable elastomers, 2. vectored injection is molded, and the difference of the crystalline rate of material and indefinite kenel leads to patent institute
Puffing shaped piece can be made by injection in the partial foaming thermoplastic elastomer (TPE) of use
1. mass expanded foams and shapes in foaming and setting mold, melt passes through melt under the thrust of Bitruder
It pumps under steady pressure and flow rate, then the melt homogeneously containing foaming agent and auxiliary addition agent is passed through into multichannel latus rectum by distributor
Moulding, which is respectively enterd, with runner respectively designs position.When homogeneous melt leaves runner and enters mold, spatial expansion and ambient pressure
Release expands melt side, side filling and cooling.Multichannel latus rectum and the discharging position of runner and latus rectum size, into the position of mold
Putting combine foaming manufactured goods moulding shape and melt temperature, and pressure, glass transition temperature or softening point temperature etc. integrate item
Part designs.Mold is that size and shape according to needed for expanded material manufactured goods are designed and are set with runner and heat tracing and temperature control
Meter.Hot melt is flowed and is filled rapidly in mold, and flux foaming and expansion in flowing and filling, and in temperature controlling instruments
Lower sizing cooling is adjusted, due to the runner of mold, temperature control is vented, and the appearance and size even ring layouts such as mouth of a river are made to control
The final expansion ratio of product, closed air bag and trepanning air passage structure, capillary penetrate through ratio and wall thickness etc. to meet the specific of downstream
Using.
2. vectored injection is molded, the difference of the crystalline rate of material and indefinite kenel leads to partial foaming used by patent
Puffing shaped piece can be made by injection in thermoplastic elastomer (TPE).When the hot melt of high pressure leaves extruding machine end runner, foaming
Agent is propelled during amplifying moment release of pressure in space on melt to profiled piece fixing piece, and melt cools down in foaming and external empty
Between the lower sizing for realizing material of temperature control and expansion ratio matching.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of preparation method of degradable poly terephthaldehyde acids expanded material, it is shown in Figure 1, include the following steps：
(1)：By 100 parts of poly terephthalic acid class plastics (the present embodiment uses PET) and 5 parts of degradation agents, (the present embodiment is adopted
With 1,4-butanediol) it puts into multiple screw extruder one, operation temperature is 230 DEG C, and shear melting forms the heat with mobility
Melt one, at this point, using the high rotating speed cutting of high temperature of screw rod, and coordinate the degradation agents such as short chain alcohol by poly terephthalic acid class plastics
Partial digestion is broken into molecule fragment, and molecule fragment is blocked by functional groups such as such as hydroxyls；
(2)：Hot melt one is pumped into screw reactor, adding 5 parts of chain extenders, (the present embodiment uses diisocyanate
The long-chain Type Polyurethane Prepolymer of sealing end is specifically obtained by dicyclohexyl methyl hydride diisocyanate HMDI and polymerization),
It is reacted at 240 DEG C, this step mainly utilizes the closed cavity in screw reactor and the screw thread of the heat exchange of energy mixed at high speed, shearing
Element, then under the action of metallic catalyst, chain extension is carried out to there are the macromoleculars of the functional groups such as hydroxyl by chain extender, and
Formed PET or PBT such as polyester-type urethano block macromolecule polyalcohol；
(3)：It is then pumped in multiple screw extruder two from the reaction melt of screw reactor outlet discharge, meanwhile, in spiral shell
0.4 portion of nucleating agent (the present embodiment uses nanometer titanium dioxide) and 5 parts of foaming agents (the present embodiment uses are added in bar extruding machine two
CO2With N2Mixture), control melt temperature be 230 DEG C, pressure 100bar, mixing the solid additives such as homogeneous, nucleating agent exist
It is thoroughly mixed in melt under the engaged element effect of the region of engagement of twin-screw, usual engaged element accounts for whole spiro rod length
15~40%, foaming agent feeds the mixed zone of Bitruder two, and under engaged element effect that melt and high pressure is critical
Gas mixing is uniform, and high pressure gas is infiltrated through melt and wrapped up centered on nucleating agent by melt；
(4)：Booster pump is entered by the melt of static mixer or dynamic mixer, booster pump will control melt outlet pressure
Power is in 180bar, and Melt Pump can provide stable pressure limit and flow accuracy.In the foaming of Melt Pump egress selection
Process routes foam and shape for mass expanded in foaming and setting mold.
Embodiment 2
As different from Example 1, the present embodiment is further adding in hot melt one in the screw reactor of step (2)
When, it also adds in and is cut in multiple screw extruder three by 97 parts of aliphatic polyester (the present embodiment uses adipic acid hexylene glycol ester) simultaneously
Cut hot melt two made of melting.
Embodiment 3-4
As different from Example 2, the aliphatic polyester of the present embodiment is changed to respectively using tetramethylene adipate and oneself
Diacid hexylene glycol butanediol ester, additive amount are also changed to 10 parts and 50 parts respectively.
Embodiment 5
Unlike embodiment, the formula of the present embodiment replaces with：0.1 part of PET, 0.01 part of degradation agent, chain extender
0.1 part, 0.01 part of nucleating agent, 0.1 part of foaming agent.
Embodiment 6
Unlike embodiment, the formula of the present embodiment replaces with：100 parts of PET, 10 parts of degradation agent, chain extender 10
Part, 1 part of nucleating agent, 10 parts of foaming agent.
Embodiment 7
It is not both that the present embodiment is also added with 10 parts of crosslinking agent nitrogen pyrroles in the inlet of multiple screw extruder two with embodiment 1
Pyridine.
Embodiment 8
It is not both that the present embodiment is also added with 5 parts of crosslinking agent HDI tri- in the inlet of multiple screw extruder two with embodiment 1
Aggressiveness.
Embodiment 9-16
Different with embodiment 8, the crosslinking agent of the present embodiment is changed to that single pyridine, toluene 2 is respectively adopted, and 4 two is different
Cyanate TDI, '-diphenylmethane diisocyanate MDI, isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI,
Dicyclohexyl methyl hydride diisocyanate HMDI, HDI trimer, poly methylene poly phenyl poly isocyanate.
Embodiment 17-21
Compared with Example 1, in addition to degradation agent to be replaced with to ethylene glycol, hexylene glycol, amine, fat two respectively in the present embodiment
Outside first acid and aromatic dibasic acid, remaining is.
Embodiment 22-24
Compared with Example 1, the overwhelming majority is all identical, in addition to replacing with chain extender using hexichol respectively in the present embodiment
Methane diisocyanate MDI, isophorone diisocyanate IPDI and hexamethylene diisocyanate HDI respectively with polyalcohol
Polymerizate.
Embodiment 25
It is different with embodiment 4, in addition to chain extender is replaced with both ends by epoxy radicals end-blocking in the present embodiment
Long chain type polymer.
Embodiment 26-31
Compared with Example 1, in addition to nucleating agent is changed to using carbon nanotube in the present embodiment, talcum powder, graphene, is changed
Property calcium carbonate, carbon black and tetrafluoroethene pulvis.
Embodiment 32-33
Compared with Example 1, in addition to foaming agent is changed to using CO in the present embodiment2、N2, normal butane, pentane and isoamyl
Alkane.
Expanded material will be made in above-described embodiment compared with the comparative example after degradation agent is removed by each Example formulations, hair
Existing, compared to each comparative example, the fusing point of the expanded material of corresponding embodiment all decreases substantially, and melting range broadens (particularly
Foaming operation time window never adds 5 DEG C or so before degradation agent substantially and improves to suitable 5-20 DEG C or so) so that it is more
Be conducive to produce the following process of piece, meanwhile, tensile strength, toughness, tearing strength etc. also improve 10-30% or so substantially.
In addition, the degradable situation of more each comparative example and embodiment, finds to add in before and after degradation agent, difference is little, substantially in 2-3
It can be achieved in or so year substantially completely to degrade.
Embodiment 34
Compared with Example 1, the overwhelming majority is all identical, in addition in the present embodiment step (1)：The operation of multiple screw extruder one
Temperature is 210 DEG C；
In step (2)：The operation temperature of screw reactor is 220 DEG C；
In step (3)：Melt temperature is controlled in multiple screw extruder two at 200 DEG C, melt pressure 70bar.
Embodiment 35
Compared with Example 1, the overwhelming majority is all identical, in addition in the present embodiment step (1)：The operation of multiple screw extruder one
Temperature is 250 DEG C；
In step (2)：The operation temperature of screw reactor is 260 DEG C；
In step (3)：Melt temperature is controlled in multiple screw extruder two at 260 DEG C, melt pressure 150bar.
Embodiment 36
As different from Example 1, the foam forming method of the present embodiment is molded using vectored injection.
Embodiment 37
As different from Example 1, PET is replaced with polypropylene terephthalate by the present embodiment.
Embodiment 38
As different from Example 2, adipic acid hexylene glycol ester is replaced with adipic acid hexylene glycol butanediol ester by the present embodiment.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously can easily make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to above-described embodiment, abilities
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be the present invention's
Within protection domain.
Claims (10)
1. a kind of degradable poly terephthaldehyde acids expanded material, which is characterized in that include the component of following parts by weight：Poly- pair
0.1-100 parts of Phthalic acids plastics, 0-97 parts of aliphatic polyester, 0-10 parts of degradation agent, 0.1-10 parts of chain extender, crosslinking agent 0-
10 parts, 0.01-1 parts of nucleating agent, 0.1-10 parts of foaming agent.
2. a kind of degradable poly terephthaldehyde acids expanded material according to claim 1, which is characterized in that described is poly-
Terephthaldehyde's acids plastics are PET, PBT or polypropylene terephthalate PTT.
A kind of 3. degradable poly terephthaldehyde acids expanded material according to claim 1, which is characterized in that the drop
Solution agent is alcohol, amine or organic dibasic acid.
A kind of 4. degradable poly terephthaldehyde acids expanded material according to claim 3, which is characterized in that the alcohol
For short chain glycol, the organic dibasic acid is binary acid or aromatic dibasic acid.
A kind of 5. degradable poly terephthaldehyde acids expanded material according to claim 1, which is characterized in that the fat
Fat adoption ester is adipic acid hexylene glycol ester, tetramethylene adipate or adipic acid hexylene glycol butanediol ester.
A kind of 6. degradable poly terephthaldehyde acids expanded material according to claim 1, which is characterized in that the friendship
Join agent and use the compound containing 2 or 2 or more crosslinkable functionalities；
The chain extender uses the length of diisocyanate terminated long-chain Type Polyurethane Prepolymer or both ends by epoxy radicals end-blocking
Chain polymer；
The nucleating agent is selected from carbon nanotube, nanometer titanium dioxide, talcum powder, modified calcium carbonate, graphene, carbon black or tetrafluoro second
At least one of alkene pulvis；
The foaming agent is selected from CO2、N2, normal butane, at least one of pentane or isopentane.
7. a kind of preparation method of degradable poly terephthaldehyde acids expanded material, which is characterized in that include the following steps：
(1)：0.1-100 parts of poly terephthalic acid class plastics and 0-10 parts of degradation agents are put into multiple screw extruder one, are sheared
Melting forms the hot melt one with mobility；
(2)：Hot melt one is pumped into screw reactor, adds 0.1-10 parts of chain extenders, is reacted；
(3)：It is then pumped in multiple screw extruder two from the reaction melt of screw reactor outlet discharge, meanwhile, it is squeezed in screw rod
0-10 parts of crosslinking agents, 0.01-1 portions of nucleating agents and 0.1-10 foaming agents are added in molding machine two, mixes homogeneous；
(4)：Then, by the output of homogeneous melt pressure and foaming obtained by step (3).
8. the preparation method of degradable poly terephthaldehyde acids expanded material according to claim 7, which is characterized in that step
Suddenly it is adding in hot melt for the moment in the screw reactor of (2), is also adding in simultaneously by being no more than 97 parts of aliphatic polyester in screw rod
Hot melt two made of three shear melting of extruding machine.
9. the preparation method of degradable poly terephthaldehyde acids expanded material according to claim 7, which is characterized in that step
Suddenly in (1)：The operation temperature of multiple screw extruder one is 210~250 DEG C；
In step (2)：The operation temperature of screw reactor is 220-260 DEG C.
10. the preparation method of degradable poly terephthaldehyde acids expanded material according to claim 7, which is characterized in that
In step (3)：Multiple screw extruder two is divided into leading portion, stage casing and back segment by melt direction of advance, wherein, the crosslinking agent is in screw rod
Two leading portion of extruding machine adds in, and nucleating agent adds in two stage casing of multiple screw extruder, and foaming agent is added in two back segment of multiple screw extruder；
Melt temperature is controlled in multiple screw extruder two at 200-260 DEG C, melt pressure 70-150bar.
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| CN112266499A (en) * | 2020-10-23 | 2021-01-26 | 江苏倍特利新材料有限公司 | Supercritical carbon dioxide foaming material and preparation method and application thereof |
| CN112323152A (en) * | 2020-10-20 | 2021-02-05 | 宁波大发化纤有限公司 | Method for preparing regenerated polyester staple fiber from spandex-containing waste polyester textile |
| CN113025007A (en) * | 2021-03-18 | 2021-06-25 | 浙江恒澜科技有限公司 | Polyester foam material and preparation method thereof |
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