CN106479134B - A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)（PBT）And preparation method thereof - Google Patents
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)（PBT）And preparation method thereof Download PDFInfo
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- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 105
- 238000004132 cross linking Methods 0.000 title claims abstract description 51
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- -1 polybutylene terephthalate Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 17
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- 238000005453 pelletization Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007605 air drying Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 14
- 229910000077 silane Inorganic materials 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000012745 toughening agent Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004756 silanes Chemical class 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 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 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims 2
- 230000008929 regeneration Effects 0.000 abstract description 8
- 238000011069 regeneration method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 3
- 230000008439 repair process Effects 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical class O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
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- Polymers & Plastics (AREA)
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Abstract
A kind of isomerism cross-linking method of crosslinking agents of POSS containing L is modified polybutylene terephthalate (PBT)（PBT）And preparation method thereof, it is related to a kind of plastic material and preparation method thereof, PBT forced air dryings under the conditions of 80 DEG C will be recycled；Homemade micro- crosslinking masterbatch are first put into Universalpulverizer and place into grinding in planetary ball mill until the grain size of crosslinking material reaches 10~50 μm, then 4~6min of high-speed mixer and mixing is put into dried recycling hard PBT, micro- crosslinking masterbatch, heat stabilizer and inorganic filler by weight ratio, finally with double screw extruder at 220 DEG C~240 DEG C extruding pelletization up to reworked material.Inorganic kernel can assign its good heat resistance, flame resistance, splendid water resistance, radiativity and electrical property, can play facilitation in process.And being introduced into the regenerative process that can make recycling PBT for isomerism cross-linking method need not add in compatilizer the toughness of regeneration PBT and intensity can also be made fine, great market popularization value.
Description
Technical field
The present invention relates to a kind of plastic material and preparation method thereof, more particularly to a kind of homogeneity of crosslinking agent containing L-POSS
Isomery cross-linking method is modified polybutylene terephthalate (PBT)（PBT）And preparation method thereof.
Background technology
Polybutylene terephthalate (PBT), English name polybutylene terephthalate（Abbreviation PBT）, belong to poly-
Ester series, is by 1.4-pbt butanediols (1.4-Butylene glycol) and terephthalic acid (TPA) (TPA) or terephthalic acid (TPA)
Ester (DMT) polycondensation forms, and translucent to opaque, crystalline thermoplastic polyester tree via milky made of program is kneaded
Fat.With being referred to as thermoplastic polyester or saturated polyester together with PET.Polybutylene terephthalate (PBT) (Polybutylene
Terephthalate) it is one of five big general engineering plastics.
In recent years, with the demand of industrial development, concern of the people to the study on the modification of PBT also more.PBT has resistance to
Wet, high temperature resistant, oil resistant, wear-resisting, resistant to chemical etching, electrical insulation capability is good, hot property is excellent, mechanical performance and processing performance are strong,
The advantages that fast is molded, is widely applied in the fields such as auto industry, electronic apparatus, mechanical equipment and optical cable and optical fiber；
PBT creeps are smaller, and high temperature resistant, performance changes very little under the high temperature conditions；The energy that production PBT is consumed is in engineering plastics
It is minimum；Heat-resistant aging is excellent.In addition, outdoor long-term ageing is also fine, unstressed cracking, solvent resistant is good；It is easy to fire-retardant, and
It is good with the affine performance of fire retardant, therefore the flame retardant products of PBT are widely applied in electronic enterprises.But PBT simultaneously
There are it is certain the defects of, mobility is very big, and heat conductivility is poor, and the product brittleness produced is big etc., therefore the modification to it
Research is also a current hot issue.
Invention content
A kind of isomerism cross-linking method the purpose of the present invention is to provide crosslinking agent containing L-POSS is modified poly- terephthaldehyde
Sour butanediol ester（PBT）And preparation method thereof, the present invention is crosslinked law technology by isomerism, and enhancing is realized while toughening
Effect, solve the problems, such as because using elastic body toughening that tensile strength is caused to decline, and the introducing of isomerism cross-linking method can
It can also make regeneration PBT that there are preferable overall mechanical properties so as to which compatilizer need not be added in the regenerative process of PBT, so as to
It can reuse, great market popularization value.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)（PBT）, it is described
L-POSS crosslinking agents be the method reacted with silane compound using L-POSS, product is the derivative of silane, synthesizing cross-linked
Agent is initially formed raw material, secondly silane generates active site so as to introduce L-POSS formation chemical reaction systems under catalytic action
It is standby go out novel silane crosslinker containing L-POSS；Its structure is：
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)
（PBT）, based on mass weight part, include following component：
Recycle 100 parts of polybutylene terephthalate (PBT)；
10~30 parts of toughener；
10~30 parts of crosslinking masterbatch；
10~20 parts of inorganic filler;
3~20 parts of heat stabilizer.
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)
（PBT）, the toughener is at least one of KT-22, KT-915.
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)
（PBT）, the crosslinking masterbatch are expected by A material B and production three step part of aqua forms.
A expects composition:Polybutylene terephthalate (PBT)
The crosslinking agent of structure novel containing L-POSS
Initiator（The different hydrogen propyl benzene (CHP) of peroxidating）
B expects composition：Polybutylene terephthalate (PBT)
Catalyst（Dibutyl tin laurate）
Antioxidant（Antioxidant 1010）
Produce aqua composition：Acid and metal oxide
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)
（PBT）, the acid produced in aqua is at least one of stearic acid, inorganic acid.
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)
（PBT）, the metal oxide produced in aqua is at least one of zinc oxide, tin oxide.
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)
（PBT）, the filler is at least one of calcium carbonate, talcum powder.
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)
（PBT）, the heat stabilizer is triphenyl phosphite.
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)（PBT）Preparation side
Method includes the following steps：
A, 95 parts of A material are weighed by mass fraction, is put into extruding pelletization in double screw extruder after 4.5 parts of B material mixing, then
Again aqua is produced with 0.5 part（Stearic acid and zinc oxide 1:1 mixture）It is uniformly mixed and is put into double screw extruder extruding pelletization shape
Into crosslinking masterbatch.
B, micro- crosslinking masterbatch in A portions are first put into Universalpulverizer and place into grinding in planetary ball mill until crosslinking
Until the grain size of masterbatch reaches 10~50 μm.
C, hard PBT material forced air drying 6~8 hours under the conditions of 80 DEG C will be recycled, it is by weight ratio that micro- crosslinking is female
Material, heat stabilizer, recycling hard PBT, inorganic filler are put into high-speed mixer and are mixed 4~6 minutes, it is made uniformly to mix；
D, it is 36 the above-mentioned material being uniformly mixed in high-speed mixer to be added to screw slenderness ratio, rotating speed 200r/
In the double screw extruder of min, in the molten state using the Strong shear power of twin-screw by the average grain diameter control of micro- crosslinking masterbatch
System is uniformly mixed at 10~50 μm, while by crosslinking material with heat stabilizer, reclaimed materials and inorganic filler, and above-mentioned mixture is squeezed
Go out to be granulated and obtain the regeneration hard PBT containing cross-linked PBT.
A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)（PBT）
Preparation method, the extruder temperature of the double screw extruder are controlled between 220 DEG C -240 DEG C.
Advantages of the present invention is with effect：
The present invention synthesizes novel silane crosslinking agent.Product is the derivative of silane, is catalyzed silane under initiation and generates
Active site and-LPOSS form polyaddition reaction, the crosslinking agent with double crosslinked actions is formed, at the same time, because of L-
POSS is different from traditional organic matter, it is using Si-O as inorganic kernel, and inorganic kernel can assign its good heat resistance, resistance to combustion
Property, splendid water resistance, radiativity and electrical property, so the novel silane crosslinking agent containing L-POSS of synthesis is in these performances
Also have greatly improved, therefore this silane crosslinker can exist under high temperature, high radiation, and it more independent than silane makees crosslinking agent
Performance is more preferable, and the cost for also directly making crosslinking agent than POSS is much smaller, cross-linking effect is more preferable, performance also gets a promotion.This is specially
This kind of crosslinking agent is applied in the study on the modification of PBT by profit, along with the introducing of isomerism cross-linking method can make the regeneration of PBT
Compatilizer need not be added in the process can also make regeneration PBT have preferable overall mechanical properties.
The present invention is crosslinked law technology by isomerism, and the effect of enhancing can be realized while toughening, solves because making
The problem of tensile strength being caused to decline with elastic body toughening, and the introducing of isomerism cross-linking method can make the regeneration of PBT
Compatilizer need not be added in journey can also make regeneration PBT have preferable overall mechanical properties, so as to reuse, pole
Has market popularization value.
The crosslinking agent with L-POSS structures in the present invention consumes oxygen in combustion process, generates some and does not have combustion
The gas of burning property（Such as N2, NH3）, can play the role of diluting organic gas, so as to reduce the play of high molecular material burning
Strong degree；After L-POSS burnings, silicon oxide compound is formed, precipitates also unburned polymer surfaces, some forms protection
Layer, plays slow down heat transfer to a certain degree, inhibits imflammable gas volatilization, obstructs fuel gas and oxygen mix effect, from
Play the role of inhibiting heat transmission, resistance to combustion to a certain extent.
Description of the drawings
Fig. 1 is the reaction equation of the synthesis high temperature resistant crosslinking agent of L-POSS and vinyltrimethoxysilane.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment 1-3, the weight distribution ratio of each component is as shown in table 1 in each embodiment.Each component is weighed by proportioning,
It is mixed 5 minutes in homogenizer, discharges, the raw material of mixture is placed in double screw extruder and makes material, the temperature of extruder
Degree is at 220 DEG C -240 DEG C, rotating speed 150r/min.Batten is prepared, by corresponding standard testing（It is shown in Table 2）Results of property is shown in Table 3.
Table 1：Formula composition (part of embodiment 1-3 and comparative example 1）
Table 2：Mechanics Performance Testing standard
Table 3：The Mechanics Performance Testing of PBT is regenerated in embodiment 1-3
From 3 embodiment 1-3 of table and the mechanical experimental results of comparative example 1, we understand：Toughening is being used merely
When agent, the tensile property of material can be reduced while improving recycling PBT impact properties；After isomerism cross-linking method,
The tensile property of recycling PBT can also be improved while improving recycling PBT impact properties with crosslinking masterbatch；Contain L-POSS simultaneously
The introducing of structure crosslinking agent also has process certain help；In addition to this, the introducing of isomerism cross-linking method can make
Compatilizer need not be added in the regenerative process of PBT by, which recycling, can also make the toughness of regeneration PBT and intensity fine；Isomerism is crosslinked
Method does not influence the bending strength and bending modulus that recycle PBT substantially.
The present invention is further illustrated above by specific embodiment, but these embodiments are only exemplary
, any restrictions are not formed to protection scope of the present invention.It will be appreciated by those skilled in the art that in the spirit without departing from the present invention
In the case of protection domain, technical solutions and their implementation methods of the present invention can be carried out a variety of equivalencings, modification or
It improves, these should all fall within the scope of protection of the present invention.Protection scope of the present invention is subject to appended claim.
Claims (8)
1. a kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)（PBT）, feature
It is, based on mass weight part, includes following component：
Recycle 100 parts of polybutylene terephthalate (PBT)；
10~30 parts of toughener；
10~30 parts of crosslinking masterbatch；
10~20 parts of inorganic filler;
3~20 parts of heat stabilizer；
The crosslinking masterbatch are made of A material B material and production aqua three parts；
A expects composition:Polybutylene terephthalate (PBT)
L-POSS crosslinking agents
Initiator, the initiator are cumyl hydroperoxide CHP
B expects composition：Polybutylene terephthalate (PBT)
Catalyst, the catalyst are dibutyl tin laurate
Antioxidant, the antioxidant are antioxidant 1010
Produce aqua composition：Acid and metal oxide；
The L-POSS crosslinking agents are the methods reacted using L-POSS with silane compound, and product is the derivative of silane,
The specific method of synthetic cross-linking agent is：Raw material is initially formed, secondly silane generates active site so as to introduce under catalytic action
L-POSS forms chemical reaction and prepares L-POSS crosslinking agents；Its structure is：
。
2. a kind of isomerism cross-linking method of crosslinking agent containing L-POSS according to claim 1 is modified poly terephthalic acid fourth
Diol ester（PBT）, which is characterized in that the toughener is at least one of KT-22, KT-915.
3. a kind of isomerism cross-linking method of crosslinking agent containing L-POSS according to claim 1 is modified poly terephthalic acid fourth
Diol ester（PBT）, which is characterized in that the acid in the production aqua is at least one of stearic acid, inorganic acid.
4. a kind of isomerism cross-linking method of crosslinking agent containing L-POSS according to claim 1 is modified poly terephthalic acid fourth
Diol ester（PBT）, which is characterized in that the metal oxide in the production aqua is at least one of zinc oxide, tin oxide.
5. a kind of isomerism cross-linking method of crosslinking agent containing L-POSS according to claim 1 is modified poly terephthalic acid fourth
Diol ester（PBT）, which is characterized in that the inorganic filler is at least one of calcium carbonate, talcum powder.
6. a kind of isomerism cross-linking method of crosslinking agent containing L-POSS according to claim 1 is modified poly terephthalic acid fourth
Diol ester（PBT）, which is characterized in that the heat stabilizer is triphenyl phosphite.
7. a kind of isomerism cross-linking method of crosslinking agent containing L-POSS according to claim 1 is modified poly terephthalic acid fourth
Diol ester（PBT）Preparation method, which is characterized in that the preparation method includes the following steps：
A, weigh 95 parts of A material by mass fraction, extruding pelletization in double screw extruder be put into after 4.5 parts of B material mixing, then again with
0.5 part of production aqua mixing, is uniformly mixed and is put into double screw extruder extruding pelletization formation crosslinking masterbatch；The production aqua is 1:
1 stearic acid and the mixture of zinc oxide；
B, the crosslinking masterbatch during A is walked first are put into Universalpulverizer and place into planetary ball mill grinding until crosslinking masterbatch
Until grain size reaches 10~50 μm；
C, polybutylene terephthalate (PBT) material forced air drying 6~8 hours under the conditions of 80 DEG C will be recycled, by weight ratio will
Crosslinking masterbatch, heat stabilizer, recycling polybutylene terephthalate (PBT), inorganic filler, toughener are put into high-speed mixer
Mixing 4~6 minutes, makes it uniformly mix；
D, it is 36 the above-mentioned material being uniformly mixed in high-speed mixer to be added to screw slenderness ratio, and rotating speed is 200r/min's
In double screw extruder, in the molten state using the Strong shear power of twin-screw by the control of the average grain diameters of crosslinking masterbatch 10~
50 μm, while crosslinking masterbatch are mixed with heat stabilizer, recycling polybutylene terephthalate (PBT), toughener and inorganic filler
Uniformly, the isomerism cross-linking method for above-mentioned mixture extruding pelletization being obtained to the crosslinking agent containing L-POSS is modified poly terephthalic acid fourth
Diol ester（PBT）.
8. a kind of isomerism cross-linking method of crosslinking agent containing L-POSS according to claim 7 is modified poly terephthalic acid fourth
Diol ester（PBT）Preparation method, which is characterized in that the extruder temperature of the double screw extruder is controlled at 220 DEG C -240 DEG C
Between.
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| CN103657456A (en) * | 2013-12-18 | 2014-03-26 | 北京工商大学 | Preparation method of ethanol-permselective POSS (polyhedral oligomeric silsesquioxanes)/silicone rubber composite membrane |
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| US7700711B2 (en) * | 2007-03-02 | 2010-04-20 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D. | Manufacturing method of ladder-like phosphorous-containing polysilsesquioxanes nanocomposite material |
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| CN104903404A (en) * | 2013-01-09 | 2015-09-09 | 株式会社大赛璐 | Curable resin composition, and cured product of same |
| CN103657456A (en) * | 2013-12-18 | 2014-03-26 | 北京工商大学 | Preparation method of ethanol-permselective POSS (polyhedral oligomeric silsesquioxanes)/silicone rubber composite membrane |
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Application publication date: 20170308 Assignee: SHENYANG XINFEIYU RUBBER PRODUCTS CO.,LTD. Assignor: SHENYANG University OF CHEMICAL TECHNOLOGY Contract record no.: X2023210000283 Denomination of invention: Homogeneous isomeric crosslinking method for modifying polybutylene terephthalate (PBT) with L-POSS crosslinking agent and its preparation method Granted publication date: 20180622 License type: Common License Record date: 20231205 |