CN1058034C - PET composite material and preparing method thereof - Google Patents
PET composite material and preparing method thereof Download PDFInfo
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- CN1058034C CN1058034C CN97122065A CN97122065A CN1058034C CN 1058034 C CN1058034 C CN 1058034C CN 97122065 A CN97122065 A CN 97122065A CN 97122065 A CN97122065 A CN 97122065A CN 1058034 C CN1058034 C CN 1058034C
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- montmorillonite
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 229920006351 engineering plastic Polymers 0.000 claims abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002657 fibrous material Substances 0.000 claims abstract 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 62
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 62
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- -1 polyethylene terephthalate Polymers 0.000 claims description 11
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000005341 cation exchange Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- 229910018512 Al—OH Inorganic materials 0.000 claims description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 claims description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 150000004010 onium ions Chemical class 0.000 claims 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims 3
- 239000002114 nanocomposite Substances 0.000 claims 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims 1
- 229910008051 Si-OH Inorganic materials 0.000 claims 1
- 229910006358 Si—OH Inorganic materials 0.000 claims 1
- 229960002684 aminocaproic acid Drugs 0.000 claims 1
- 238000010009 beating Methods 0.000 claims 1
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229960002449 glycine Drugs 0.000 claims 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 230000008025 crystallization Effects 0.000 abstract description 11
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 2
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 32
- 239000010410 layer Substances 0.000 description 12
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 4
- 229910052604 silicate mineral Inorganic materials 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000001014 amino acid Nutrition 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
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N 2-Amino-2-Deoxy-Hexose Chemical compound NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UOHUDFHWFDUDID-UHFFFAOYSA-N [Cl].C[SiH](C)C Chemical compound [Cl].C[SiH](C)C UOHUDFHWFDUDID-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a polyethylene glycol terephthalate (PET) composite material and a preparation method thereof. The polyethylene glycol terephthalate (PET) composite material is used for engineering plastics, thin film materials and fiber materials, and has the advantages of high crystallization velocity, good mechanical property, good heat resistance and high size stability. Layer silicate after halogen silicane end sealing and organic * ion exchange treatment is added in any stage before the procedure of pulping to polycondensation is completed in the process of PET preparation in order to obtain the organic-inorganic composite material. The composite material prepared by the method achieves electrostatic combination between the layer silicate and PET molecules, and is uniformly dispersed in a PET substrate in nanometer size.
Description
The present invention relates to a kind of energy rapid crystallization, the good REINFORCED PET matrix material of good mechanical property, thermotolerance and dimensional stability is arranged.Be particularly related to matrix material of PET and layered silicate and preparation method thereof.
Polyethylene terephthalate (PET) is a kind of macromolecular material that is widely used in fiber, film and engineering plastics.But because PET is slow from molten state crystallization speed, heat-drawn wire is low, has limited its application in some aspects.
In order to improve the crystallization speed of PET, add the existing a lot of reports of method of organic or inorganic nucleator.But, because the nucleation efficient of inorganic nucleator is poor, and the shortcoming of the heat retention poor stability of organic nucleating agent.People just constantly seek to improve the novel method of PET crystallization velocity.Japanese kokai publication hei 8-199048 reported by after the fluoronated mica layer silicate mineral is carried out intercalation processing, prepares with PET and the method that has a polyolefine melt blending of epoxy group(ing) that crystallization velocity is fast, the method for the PET resin combination of heat retention good stability.But this method has increased the melt-processed number of times, and it has not only increased tooling cost, and inevitably causes the thermal destruction of PET.Influence the final performance of material.Te Kaiping 8-120071 reported in the process of preparation PET, in the initial stage of polycondensation, adds the method for PET resin combination of method processing machinery intensity, toughness, thermotolerance and the excellent size stability of fluoronated mica mineral and protonic acid.Though this method has reached the homodisperse of inorganics, improved mechanical property and the thermal characteristics of PET.But, do not have the chemical bond combination between inorganics and the PET.Therefore, when silicate mineral content is higher, will damage its some mechanical property.
The purpose of this invention is to provide a kind of new PET matrix material.This matrix material contains:
PTA or DMT 100 (weight part)
EG 43-77 (weight part)
Layered silicate 0.005-15 (weight part)
Halogen silane end-cappers 0.00005-1.5 (weight part)
Organic ion exchanger 0.001-1.0 (weight part)
Other additive 0-5.0 (weight part)
Wherein the most probable dispersion size of layer silicate mineral in PET is 30-50nm, and layered silicate and PET are intermolecular with the static combination.
PET matrix material of the present invention can begin preparation from terephthalic acid (PTA) and ethylene glycol (EG) or from dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG).
In PET matrix material of the present invention, the layer silicate mineral that is adopted can be Li-polynite or K-polynite or Na-polynite or Ca-polynite.Its particle diameter can be all by 300 order mesh screens, non-polynite foreign matter content＜10%.They all have swelling, and interlayer has tradable positively charged ion Li
+, K
+, Na
+, Ca
2+, Mg
2+Deng.Its cation exchange capacity (CEC) should be at 30-180meq/100g, and exchange capacity is relatively good at 50-150meq/100g, preferably at 70-120meq/100g.Consider that from the angle that reduces production costs maximum cation exchange capacity is controlled at 120meq/100g.Exchange capacity is lower than 30meq/100g, the bonding force of PET and silicate layer just a little less than, cause the mechanical property of matrix material undesirable.
In matrix material of the present invention, the content of polynite is 0.005-15 part (weight part).Polynite content is lower than 0.005 part, the enhancement deficiency, and also nucleating effect is also not obvious.When content was higher than 15 parts, the toughness of material had bigger decline.The content of polynite is relatively good 0.5-10 part.The purposes difference, the content of polynite is also different.As the matrix material that engineering plastics are used, the content of polynite is 1-10 part; Make filamentary material usefulness and then be 0.1-3 part; Make film with being 0.005-2 part.
In matrix material of the present invention, used polynite is an enhydrite.Its structure is two drift angles Si-O tetrahedrons inwardly, therebetween a slice Al-(O, OH) the octahedra unit cell of forming.Structure cell is parallel and repeatedly puts.Its octahedron can be regarded oxyhydrogen aluminum stone (Al as
2(OH)
6) layer, per three oxygen by two vacation six side's network summits of being formed by Si-O of (OH) are wherein replaced, and tetrahedron leans on shared Sauerstoffatom to be connected with octahedra.There is Al-OH to exist in the structure cell.It causes the polynite cohesion easily, and forms larger particles.Cause composite property decline and can't carry out spinning.So, must be to the Al-OH termination process, promptly through being crushed to the polynite more than 300 orders, after the thorough drying, with containing halosilanes: be selected from-chlorine trimethyl silane or dichlorodimethylsilane or METHYL TRICHLORO SILANE combination treatment.The add-on that contains halosilanes is the 1-10% of polynite consumption, and 2-8% is better, and 3-6% is best.
In matrix material of the present invention, the exchangeable cation Li between used cheating engaging layer
+, K
+, Na
+, Ca
2+, Mg
2+Handle through the organic ion exchange Deng need.Its organic ion exchanger is the hydramine ion, or the amino acid ion.Hydramine is the one-level hydramine, be selected from monoethanolamine, aminopropanol; Or the secondary hydramine, be selected from N-methylamino ethanol, diethanolamine; Or tertiary alcohol amine, be selected from the N-dimethylaminoethanol, trolamine.Amino acid is Padil or alanine or hexosamine or aminoundecanoic acid.The protonating agent for preparing described organic ion can be organic acid or mineral acid, is selected from P-hydroxybenzoic acid, terephthalic acid, m-phthalic acid, boric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, sulfuric acid.
The solvent that polynite and organic ion exchange are handled can be water, methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, butyleneglycol and their mixture.Wherein water is the best swelling agent of polynite.Polynite is at water and 1: 4-4: in 1 the water and the mixed solvent of ethylene glycol fabulous dispersiveness is arranged, ion-exchange speed is the fastest.But,, can influence the polyreaction of PET owing to a large amount of existence of water in the system.So must remove.Remove the method for anhydrating and to adopt straight run distillation, centrifugation and fractionated method.The former is simple to operate.Centrifugation adds that the method for filtration washing can be effectively except that anhydrating and other impurity, and it is more firm that ion is combined with cheating engaging layer.Also can remove and anhydrate with fractionated method.
In matrix material of the present invention, the unit cell bed thickness of polynite is 1nm, and layer width is about 100nm, and interlamellar spacing is 0.2-0.5nm.After the organic ion exchange was handled, interlamellar spacing was expanded as 1.5-3nm.One end of organic ion is that static combines with cheating engaging layer, and the reactive functionality of the other end participates in the polyreaction of PET.
In matrix material of the present invention, other additive is reactive flame retardant or matting agent or whitening agent.The purpose of adding them is for permanent fire-retardant, the delustring that increases this matrix material, brightens function.Its addition is respectively 2-3.5 part; 0.5-1.0 part; 0.1-0.5 part.
On the other hand, the present invention also provides the method for this Novel PET matrix material of preparation.This method is included in the process of preparation PET, the arbitrary stage before finishing from the polycondensation of pulling an oar, exchange the swelling polynite of handling but add through halosilanes end-blocking and organic ion, and be prepared into the PET matrix material.It is to utilize esterification or the polycondensation that participates in the PET preparation process through the polynite of halosilanes end-blocking and organic ion exchange processing, struts in the process that the PET molecular chain increases and then cheating engaging layer, reaches nano level and disperses.And, realize organic and inorganic material bonded new technology by the Coulombian charge effect.Prepare that crystallization velocity is fast, the PET matrix material of good mechanical property, thermotolerance and excellent size stability.
The preparation of PET matrix material of the present invention can be begun by PTA and EG; Also can be begun by DMT and EG, any stage before treated polynite can be finished from the polycondensation of pulling an oar adds reaction system, but adds best in earlier stage in polycondensation.Preparing this matrix material 1. can adopt. continuous polymerization.Or 2. .PTA direct esterification, gap polycondensation method.Or 3. .DMT ester-interchange method different process technological line.
The reaction mechanism and the pure PET that adopt the present invention to prepare the PET matrix material do not have tangible difference.Therefore do not need to add special catalyst.When adopting the DMT method, transesterification catalyst remains the acetate of manganese, magnesium, zinc etc., and its consumption is also suitable with the pure PET of preparation.Polycondensation catalyst still is Sb (CH commonly used
3COO)
3Or Sb
2O
3When polynite content≤5%, its molecular weight and distribute and be not subjected to the influence of polynite content can prepare the PET matrix material of higher molecular weight and narrower molecular weight distribution.
With the PET matrix material of method preparation of the present invention, observe, measure through high resolution transmission electron microscopy, confirm that the dispersion of polynite in PET reaches nano-scale.The most probable layer thickness distribution is 30-50nm.
There is stronger statcoulomb power to combine between PET macromole and the silicate layer.Therefore, they are the true solution state in phenol/tetrachloroethane solvent.
The kinetics of crystallization of PET matrix material of the present invention studies show that it can increase substantially the crystallization velocity of PET.The isothermal crystal semi-period has improved about five times than PET; The supercooling temperature of nonisothermal crystallization improves 15-17 ℃.Therefore, the matrix material for preparing with the present invention carries out the injection-molded man-hour that adds, and die temperature can be reduced to 50-70 ℃.This just provides necessary condition for developing its application in the engineering plastics field.
Because the nano-dispersed of polynite and the Chemical bond between the organic-inorganic are significantly improved mechanical property, thermotolerance and the dimensional stability of PET matrix material.
The PET matrix material of the present invention's preparation can adopt common melt processing to be processed into fiber.This matrix material is in the spun filament that obtains under the speed of spinning of 2000m/min, 3.2 times of drawing-offs, and 180 ℃ of typings, the initial modulus of gained fiber is higher more than 60% than pure PET.Dried, damp and hot contraction obviously reduces.Indicate its application prospect in PET industrial fiber field.
Preparing the PET-montmorillonite composite material with the present invention can add reactive flame retardant and prepare permanent fire-retardant PET composition.If add the XPM-1000J phosphorated reactive flame retardant of 2.8 parts (weight parts), its limited oxygen index LOI 〉=32; After flame time is 2-3 second.And molten drop phenomenon can suppress to burn effectively the time.
Embodiment 1
With cation exchange capacity is 5 parts of the Na-polynites of 90meq/100g, dry back directly with 0.25 part-processing of chlorine trimethyl silane.Then, place dispersion cup, add 50 parts of water, high-speed stirring 1 hour.Add the phosphoric acid of 0.5 part of N-dimethylaminoethanol and 0.5 part, continue stirring 2 hours.Add 40 parts of ethylene glycol, stir decompression down, heat and slough water, stand-by.
500 parts of DMT, 370 parts of EG, 0.3 part of transesterification catalyst, reaction is 3-4 hour in about 240 ℃.Add 0.4 part of Sb (CH
3COO)
3And thermo-stabilizer and above-mentioned native liquid.Reaction is 3-4 hour under 260-280 ℃ and vacuum.Obtain the PET matrix material section of montmorillonoid-containing 1%.Its [η]=0.64dl/g (phenol-tetrachloroethane of 1: 1,30 ℃); T
m=258 ℃.Under this section vacuum, behind the heat drying, injection-molded, die temperature 50-70 ℃, obtain surfacing, slick injection batten.For measuring mechanical property.Get after above-mentioned section adds 25% glass fibre, press similarity condition injection batten, for measuring mechanical property.The results are shown in Table one.
Embodiment 2
With cation exchange capacity is 90meq/100g, through 12.9 parts of the Na-of hydroxy-end capped processing polynites, places dispersion cup, adds 130 parts of 1: 1 water and ethylene glycol mixtures, high-speed stirring 1 hour.Add 1.3 parts of N-dimethylaminoethanols and phosphatase 11 .3 part, continue to stir 2 hours.Vacuum fractionation mixes with 240 parts of PTA and 50 parts of EG after sloughing water, stirs 40 minutes.Slowly adding about 240 minutes has in the esterifying kettle of 240 parts of esterifying liquids, carries out the direct esterification reaction.Then, behind heat filtering, change polycondensation vessel over to, add 0.3 part of Sb (CH
3COO)
3And thermo-stabilizer.Under 260-280 ℃ and vacuum, reacted 3-4 hour.Obtain the PET matrix material section of montmorillonoid-containing 2.5%.Its [η]=0.70dl/g (phenol-tetrachloroethane of 1: 1,30 ℃); T
m=258 ℃.The gained section is carried out melt-spinning on general spinning-drawing machine behind vacuum, heat drying.Spin fast 2000m/min.Spun filament is through drawing-off and 180 ℃ of heat setting types.The fine density 384dtex of fiber; Breaking tenacity 4CN/dtex; Elongation at break 30%; Boiling water shrinkage is 2% (30min); (180 ℃ is 8% 30min) to dry shrinkage; Initial modulus is 88CN/dtex; The PET fiber that does not add polynite that obtains under the same conditions then is respectively 390; 4.3; 28; 8%; 18%; 55.Get dried this section, injection-molded, die temperature 50-70 ℃, obtain surfacing, slick injection batten.For measuring mechanical property.Get after above-mentioned section adds 25% glass fibre, press similarity condition injection batten, for measuring mechanical property.The results are shown in Table one.
Embodiment 3
With cation exchange capacity 90meq/100g, through 25.8 parts of the Na-of hydroxy-end capped processing polynites, place dispersion cup, add 260 parts of water, high-speed stirring 1 hour.Add 2.6 parts of 2.6 parts of N-dimethylaminoethanols and phosphoric acid, continue to stir 2 hours.Centrifugation in 4000 rev/mins supercentrifuge removes by filter clear liquid.Precipitation washes twice with water, the centrifugal clear liquid of telling.Throw out mixes with 240 parts of PTA and 107 parts of EG, stirs 40 minutes.Slowly adding about 240 minutes has in the esterifying kettle of 240 parts of esterifying liquids, carries out the direct esterification reaction.Then, behind heat filtering, change polycondensation vessel over to, add 0.3 part of Sb (CH
3COO)
3And thermo-stabilizer.Under 260-280 ℃ and vacuum, reacted 3-4 hour.Obtain the PET matrix material section of montmorillonoid-containing 5%.Its [η]=0.65dl/g (phenol-tetrachloroethane of 1: 1,30 ℃); T
m=257 ℃.The gained section is behind vacuum, heat drying, and is injection-molded, die temperature 50-70 ℃, obtains surfacing, slick injection batten.For measuring mechanical property.Get after the section of above-mentioned resin adds 25% glass fibre, press similarity condition injection batten, for the mensuration mechanical property.The results are shown in Table 1.
Comparative Examples 1
500 parts of DMT, 370 parts of EG, 0.3 part of transesterification catalyst, reaction is 3-4 hour in about 240 ℃.Add 0.4 part of Sb (CH
3COO)
3And thermo-stabilizer.Reaction is 3-4 hour under 260-280 ℃ and vacuum.Obtain the PET section.Its [η]=0.66dl/g (phenol-tetrachloroethane of 1: 1,30 ℃); T
m=260 ℃.Under this section vacuum, behind the heat drying, injection-molded, 130 ℃ of die temperatures obtain surfacing, slick injection batten.For measuring mechanical property.Get after above-mentioned section adds 25% glass fibre, press similarity condition injection batten, for measuring mechanical property.The results are shown in Table one.
Table one .PET and PET composite property
Annotate 1: loading is 18.6Kg/cm
2Annotate 2:NPET-1; NPET-2.5; NPET-5 is respectively and contains 1%; 2.5%; The PET matrix material of 5% polynite.
| Sample number into spectrum | Shock strength J/m | Bending strength Mpa | Composite bending modulus Gpa | Tensile strength Mpa | HDT ℃ | Crystallization supercooling temperature ℃ |
| PET | 58 | 70 | 195 | |||
| NPET-1 1 | 20.3 | 104.5 | 2.3 | 65 | 88 | 208 |
| NPET-2.5 2 | 18.4 | 101 | 2.5 | 82 | 110 | 212 |
| NPET-5 2 | 15.5 | 72.9 | 2.6 | 84.3 | 120 | 210 |
| The NPET-1+25% glass | 48.4 | 104.9 | 5.6 | 62 | 230 | |
| NPET-2.5+25% glass | 41.3 | 93.1 | 7.3 | 88 | 235 |
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122065A CN1058034C (en) | 1997-12-22 | 1997-12-22 | PET composite material and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122065A CN1058034C (en) | 1997-12-22 | 1997-12-22 | PET composite material and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1183434A CN1183434A (en) | 1998-06-03 |
| CN1058034C true CN1058034C (en) | 2000-11-01 |
Family
ID=5176657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122065A Expired - Lifetime CN1058034C (en) | 1997-12-22 | 1997-12-22 | PET composite material and preparing method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1058034C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2816364C1 (en) * | 2023-06-21 | 2024-03-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" (КБГУ) | Method for producing complex stabilizer for synthesis of polyethylene terephthalate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6855404B2 (en) * | 2003-03-13 | 2005-02-15 | E. I. Du Pont De Nemours And Company | Inorganic sheet laminate |
| CN102827494A (en) * | 2012-08-16 | 2012-12-19 | 费正新 | Organosilicon modified talcum powder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03215557A (en) * | 1990-01-19 | 1991-09-20 | Ube Ind Ltd | Resin composition |
| JPH08120071A (en) * | 1994-10-24 | 1996-05-14 | Unitika Ltd | Production of reinforced polyester resin composition |
| JPH08199048A (en) * | 1995-01-23 | 1996-08-06 | Mitsubishi Chem Corp | Polyethylene terephthalate resin composition |
-
1997
- 1997-12-22 CN CN97122065A patent/CN1058034C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03215557A (en) * | 1990-01-19 | 1991-09-20 | Ube Ind Ltd | Resin composition |
| JPH08120071A (en) * | 1994-10-24 | 1996-05-14 | Unitika Ltd | Production of reinforced polyester resin composition |
| JPH08199048A (en) * | 1995-01-23 | 1996-08-06 | Mitsubishi Chem Corp | Polyethylene terephthalate resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2816364C1 (en) * | 2023-06-21 | 2024-03-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" (КБГУ) | Method for producing complex stabilizer for synthesis of polyethylene terephthalate |
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| CN1183434A (en) | 1998-06-03 |
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Assignee: China Textile Academy Shaoxing Jiangnan Branch, China Textile Academy Co., Ltd. Assignor: Chinese Textile Scientific Research Inst. Contract fulfillment period: 2007.10.14 to 2013.10.13 contract change Contract record no.: 2008990001158 Denomination of invention: PET composite material and preparing method thereof Granted publication date: 20001014 License type: Exclusive license Record date: 20081110 |
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