CN1224640C - Method for preparing uvioresistant polyester by nanometer titania in situ - Google Patents
Method for preparing uvioresistant polyester by nanometer titania in situ Download PDFInfo
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- CN1224640C CN1224640C CN 200310122743 CN200310122743A CN1224640C CN 1224640 C CN1224640 C CN 1224640C CN 200310122743 CN200310122743 CN 200310122743 CN 200310122743 A CN200310122743 A CN 200310122743A CN 1224640 C CN1224640 C CN 1224640C
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- 229920000728 polyester Polymers 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 90
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 230000005855 radiation Effects 0.000 claims abstract description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000004576 sand Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000009388 chemical precipitation Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 150000004645 aluminates Chemical class 0.000 claims 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- OVPXRLUTUWRYEY-UHFFFAOYSA-N dimethyl naphthalene-1,8-dicarboxylate Chemical compound C1=CC(C(=O)OC)=C2C(C(=O)OC)=CC=CC2=C1 OVPXRLUTUWRYEY-UHFFFAOYSA-N 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 238000009987 spinning Methods 0.000 abstract description 9
- 239000004744 fabric Substances 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 238000009941 weaving Methods 0.000 abstract description 2
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- 206010013786 Dry skin Diseases 0.000 description 13
- 239000000805 composite resin Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910000989 Alclad Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 229920001634 Copolyester Polymers 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 210000003491 skin Anatomy 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical class OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000009759 skin aging Effects 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical compound C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 description 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical class COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 206010064127 Solar lentigo Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 230000004054 inflammatory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 201000008261 skin carcinoma Diseases 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
一种利用纳米二氧化钛原位制备抗紫外线辐射聚酯的方法，属于复合材料领域。方法如下：首先采用纳米二氧化钛为紫外线屏蔽剂，然后对其进行无机/有机复配表面改性，使其能均匀分散在聚酯聚合的单体之一即二元醇中，然后将配好的纳米二氧化钛/二元醇浆料通过高速分散与循环砂磨处理到纳米氧化钛的平均粒径小于50纳米，最后与聚酯其他单体进行聚合或者共聚，在聚合过程中原位得到抗紫外纳米二氧化钛/聚酯复合材料。由此复合材料纺丝织造得到织物的紫外线屏蔽指数大于50，将材料制成薄膜的紫外线屏蔽率大于99%，在紫外线照射1000小时后，力学性能下降幅度小于5%，该复合材料可用在纤维、薄膜与工程塑料等领域，提高材料对紫外线的屏蔽与抗老化能力。The invention discloses a method for preparing anti-ultraviolet radiation polyester in situ by using nano-titanium dioxide, which belongs to the field of composite materials. The method is as follows: firstly, nano-titanium dioxide is used as an ultraviolet shielding agent, and then its inorganic/organic composite surface is modified so that it can be uniformly dispersed in one of the monomers of polyester polymerization, that is, glycol, and then the prepared The nano-titanium dioxide/glycol slurry is processed through high-speed dispersion and circular sand milling until the average particle size of nano-titanium oxide is less than 50 nanometers, and finally polymerized or copolymerized with other polyester monomers to obtain UV-resistant nano-titanium dioxide in situ during the polymerization process / polyester composite. The ultraviolet shielding index of the fabric obtained by spinning and weaving of the composite material is greater than 50, and the ultraviolet shielding rate of the film made of the material is greater than 99%. After 1000 hours of ultraviolet radiation, the decline in mechanical properties is less than 5%. The composite material can be used in fiber , film and engineering plastics and other fields, improve the material's ability to shield against ultraviolet rays and anti-aging.
Description
Technical field
The present invention relates to a kind of preparation method of polyester, particularly a kind of method of utilizing nano titanium oxide in-situ preparing anti-ultraviolet radiation poly ester.Belong to field of compound material.
Technical background
In recent years, because forest vegetation is destroyed aggravation, Sunspot Activities is frequent and factors such as a large amount of uses freon refrigerant make the mankind be faced with enhanced ultraviolet radiation day by day, ultraviolet ray be divided into UVC (200～280nm), UVB (280～320nm), UVA (320～400nm) three districts.UVC is absorbed by ozonosphere, to the basic not damaged effect of human body.UVB can be absorbed by dermis of skin, and permanent irradiation erythema, inflammation, skin aging can occur, can cause skin carcinoma when serious.The UVA penetrance is dark more than UVB, can make skin pitch-dark, and long-term accumulation will cause skin aging.Simultaneously, the energy that ultraviolet ray has is about 314～419KJ/mol, is enough to destroy chemical bond, the initiation autoxidation reaction of polymkeric substance, causes the degradation with aging of polymkeric substance such as plastics, rubber, coating resin, and the loss that therefore cause every year is huge.
At present, the polyester with the ageing-resistant function of uvioresistant mainly adopts interpolation uvioresistant additive to carry out the preparation of blended melting method.The uvioresistant additive is divided into organic and inorganic two big classes.Inorganic UV shield agent becomes research and uses focus with characteristics such as the chemistry of its brilliance and thermostability, non-migrating, tasteless, nontoxic, nonirritants.Find by literature search, Chinese patent application number is: 00816956.X, name is called: contain m-phthalic acid, 1, the copolyester of 4-cyclohexanedimethanol and ultraviolet absorber compounds and by its goods of making, publication number is: 1409737, this patent disclosure a kind of copolyester blend of anti-ultraviolet radiation, it comprises having 1, the polyethylene terephthalate base copolyester of 4-cyclohexanedimethanol: significant quantity be selected from benzoxazinone, dimeric benzotriazole, the ultraviolet radiation absorber of triazine and composition thereof, through uviolizing after 1536 hours, the colour-change of sheet material is littler 3.4 times than unmodified with the copolyester blend sheet material of this method preparation.But this method has certain toxicity owing to adopted the UV light absorber of organic class, and their less stable in resin matrix are decomposed in material processing easily simultaneously, and the heat resistance of goods is restricted.Simultaneously skin there is pungency, is not suitable for being applied to fields such as weaving, packaging film.
Summary of the invention
The present invention is directed to the problems referred to above that exist in the background technology, propose a kind of method of utilizing nano titanium oxide in-situ preparing anti-ultraviolet radiation poly ester, make it solve above deficiency.The present invention has at first abandoned organic class UV light absorber, but adopt the inorganic nano ultraviolet screening agent, overcome traditional blend melt spinning method fully and existed UV light absorber and in polymkeric substance, reunite and disperse disadvantages such as intensity irregular, material is low, heat resistance difference, overcome deficiencies such as back finishing technique fabric feeling, ventilative, wearing comfort and function weather resistance be not good.The uvioresistant polyester that the inventive method makes is compared with conventional polyester, and the processibility of material, mechanical property and resistance toheat are unaffected, the remarkable long-acting environment friendly of uvioresistant effect.
The present invention is achieved by the following technical solutions, the preparation method that the present invention proposes polyester is as follows: at first adopting nano titanium oxide is ultraviolet screening agent, then it is carried out inorganic/organic complex surface modification, with organic agent or coupling agent nano titanium oxide is carried out surface organic modification, carry out inorganic modified with surface bag silicon alclad to nano titanium oxide, make it can be dispersed in one of monomer of polyester--in-the dibasic alcohol, by metering the nano titanium oxide/dibasic alcohol slurry for preparing is arrived the median size of nano-titanium oxide less than 50 nanometers by high speed dispersion and circulation sanded then, last and other monomers of polyester carry out polymerization or copolymerization, and original position obtains having good mechanics in polymerization process, anti-ultraviolet nano titanium dioxide/the polyester composite of thermal property.
This material can be used for preparing antiultraviolet fiber, film and various ageing-resistant injection moulding polyester articles etc.Thus the matrix material spinning weave the fabric that obtains the ultraviolet screener index greater than 50, material is made the rate of ultraviolet shield of film greater than 99%.After 1000 hours, the mechanical properties decrease amplitude is less than 5% in uviolizing for material.
Below method of the present invention is done further to limit, concrete steps are as follows:
(1) nano-titanium oxide is carried out the surface inorganic coating modification, at first adopting chemical precipitation method to coat thickness on the nano-titanium oxide surface is the silicon-dioxide of 5 nanometers, adopt equally then and carry out alumina-coated on the nano-titanium oxide of chemical precipitation method after wrapping silicon-dioxide again, coating layer also is 5 nanometers, obtains the modified Nano titanium oxide of surface bag silicon alclad at last.
(2) will be dispersed in 95% the ethanolic soln through inorganic modified nano-titanium oxide, the mass percentage content of nano-titanium oxide is 20%, with polymer organic treatment agent or coupling agent it is carried out surface organic modification again, consumption is 3～15% of a nano-titanium oxide, and washing and filtering places 1 hour dry for standby of 100 ℃ of baking ovens.
(3) with above-mentioned process inorganic/nano-titanium oxide of organic complex modification is dispersed in the dibasic alcohol, solid content is 5～30% mass percents, at first adopt high speed dispersor that nano-titanium oxide/dibasic alcohol slurry is mixed, use sand mill that slurry is ground dispersion till the titanium oxide particle diameter reaches below 50 nanometers then, detect with laser particle analyzer.
(4) another monomer of the nano-titanium oxide that above-mentioned steps is obtained/dibasic alcohol slurry and polyester---aromatic binary carboxylic acid carries out polyreaction under the condition that has catalyzer and stablizer to exist, the nano-titanium oxide addition of modification accounts for 0.5%～5% of polyester total amount, according to the different field that final material is used, original position obtains the nano-titanium oxide/polyester composite of different molecular weight.
Nano-titanium oxide of the present invention is a rutile crystal type, particle diameter 10～30 nanometers.Described bag silicon is handled and is adopted acid to drip chemical precipitation method, is presoma with the water glass, and the metering of silicon-dioxide quality percentage ratio is 5～10% of nano-titanium oxide.Described alclad is handled and is adopted alkali to drip chemical precipitation method, is presoma with Tai-Ace S 150, and the metering of aluminum oxide quality percentage ratio is 3～8% of nano-titanium oxide.
Polymer organic treatment agent of the present invention is a polyoxyethylene glycol, one or more in polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, the polyacrylamide.Described coupling agent is meant silane coupling agent, one or more in titanate coupling agent and the aluminic acid ester.
The dibasic alcohol of polyester of the present invention is a kind of in ethylene glycol, propylene glycol, the butyleneglycol, and another kind of monomer can be one or more in dimethyl terephthalate (DMT), terephthalic acid, dimethyl isophthalate, naphthalene two dimethyl phthalates.
Nano-titanium oxide through modification of the present invention can participate in the polyester reaction separately, also can together carry out polyreaction with chemical fibre of titanium dioxide.
In-situ polymerization of the present invention prepares nano-titanium oxide/polyester composite and can be used on fields such as fiber, film and engineering plastics.
Compared with prior art, that the present invention at first selects for use is nontoxic, the stabilized nano titanium oxide is as ultraviolet screening agent, and it is carried out having suppressed behind the surface bag silicon photocatalytic activity of nano-titanium oxide, can improve the ageing-resistant performance of goods, adopt surperficial bag rate to improve dispersiveness in the dibasic alcohol of nano-titanium oxide in addition, adopt surface organic modification, can reduce the catalytic activity of nano-titanium oxide greatly, improve PET hue the polyester degraded.It is worthy of note that the present invention adopts in-situ polymerization, solved the agglomeration traits of nano titania particle in matrix, truly realized nanometer homodisperse effect.Nano-titanium oxide/polyester composite of obtaining of method can be used for preparing antiultraviolet fiber, film and various ageing-resistant injection moulding polyester articles etc. thus.Thus the matrix material spinning weave the fabric that obtains the ultraviolet screener index greater than 50, material is made the rate of ultraviolet shield of film greater than 99%.
Embodiment
Provide following examples in conjunction with content of the present invention:
Embodiment 1
Have at 5000mL that to add concentration in the glass reaction still of recirculated water chuck under condition of stirring be that the sodium silicate aqueous solution 2500mL of 0.2molL (presses SiO
2: TiO
2=10%, mass percent), add 500mL deionized water and 30 gram Sodium hexametaphosphate 99s again, heated and stirred 30 minutes, after treating that Sodium hexametaphosphate 99 all dissolves, adding 300 gram median sizes is the rutile type nano titanium oxide of 10 nanometers, aqueous sodium hydroxide solution regulator solution pH value with 1molL is 9.5 ± 1, heat up and stir, when temperature rose to 85 ℃, the continuous dropping of beginning concentration was 10% aqueous sulfuric acid (mass percent), rate of addition is always 9.5 ± 1 with the pH value of keeping reaction solution, after 45 minutes, stop to drip sulfuric acid, the insulation ageing adds analytical pure sulfuric acid aluminium 50 gram backs and (presses Al in reaction solution after 5 hours
2O
3: TiO
2=5%, mass percent), the solution pH value becomes about 2～3, under 85 ℃ of situations, the aqueous sodium hydroxide solution of Dropwise 5 % stops to drip after the reaction soln pH value is 8.5 in 45 minutes, continues insulation ageing 2 hours, filter, wash 3 times after, place 100 ℃ of baking oven dry for standby.
The ethanol of adding 95% in the 2000mL beaker, stir and add 30 gram polyvinylpyrrolidones down, be heated to 70 ℃, after treating that polyvinylpyrrolidone dissolves fully, get the above-mentioned nano-titanium oxide of handling through bag silicon alclad and it is pulverized, and weighing 300 grams place above-mentioned ethanolic soln with stirrer, at 70 ℃ of following stirring reactions after 1 hour, filter, after washing is placed on and activates 1 hour in 100 ℃ of baking ovens, dry for standby.
Above-mentioned nano-titanium oxide through inorganic/organic common modification is dispersed in 1500mL ethylene glycol, and to be made into concentration be 20% slurry, at first in high speed dispersor with its dispersion, in the recirculation system sand grinding machine, grind then, in the process of lapping slurry is carried out testing graininess with laser particle analyzer, when the mean particle size of nano-titanium oxide in the slurry during less than 50 nanometers, stop to grind, the discharging slurry is standby.
8000g terephthalic acid, 3812g ethylene glycol and above-mentioned nano-titanium oxide slurry 235 grams are together added in 30 liters of polyester stills the making beating back, use antimony glycol to be polymerization stabilizer, carry out polyreaction as polycondensation catalyst, trimethyl phosphite 99.Feed nitrogen, the esterification of this process is carried out under 0.2Mpa pressure, polycondensation final stage still internal pressure should remain below 80Pa.Keep high vacuum discharging after 220 minutes, obtain nano-titanium oxide/polyester composite.The form and aspect L value 82.82 of resin, form and aspect b value 3.59, limiting viscosity are 0.680,260.8 ℃ of fusing points, carboxyl-content are 20mol.t
-1, glycol ether content is 0.9%.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 50.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.9%.
Embodiment 2
According to embodiment 1 described method, different is to carry out the surface bag silicon of nano-titanium oxide by SiO
2: TiO
2=5%, mass percent, alclad is pressed Al
2O
3: TiO
2=3%, mass percent, the polyvinylpyrrolidone consumption is 15% of a nano-titanium oxide consumption.
According to nano-titanium oxide/polyester composite that embodiment 1 described method prepares, the form and aspect L value 80.10 of resin, form and aspect b value 6.07, limiting viscosity are 0.660,260.1 ℃ of fusing points, carboxyl-content are 20mol.t
-1, glycol ether content is 0.8%.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 50.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.14%.
Embodiment 3
According to embodiment 1 described method, different is to carry out the surface bag silicon of nano-titanium oxide by SiO
2: TiO
2=8%, mass percent, alclad is pressed Al
2O
3: TiO
2=8%, mass percent.
According to nano-titanium oxide/polyester composite that embodiment 1 described method prepares, the form and aspect L value 81.65 of resin, form and aspect b value 5.66, limiting viscosity are 0.659,262.7 ℃ of fusing points, carboxyl-content are 19mol.t
-1, glycol ether content is 1.1%.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 50.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.12%.
Embodiment 4
Carry out the inorganic/organic surface modifying of nano-titanium oxide according to embodiment 1 described method, different is, and to carry out organically-modified agents useful for same be polyoxyethylene glycol, and consumption is 3% of a nano-titanium oxide consumption, and other processing modes are all identical with temperature of reaction.
Be dispersed in the ethylene glycol according to the nano-titanium oxide of embodiment 1 described method with modification, different is that solid content of slurry is 5%.
8000g dimethyl terephthalate (DMT), 944g ethylene glycol and above-mentioned nano-titanium oxide slurry 4388 grams are together added in 30 liters of polyester stills the making beating back, use antimony glycol to be polymerization stabilizer, carry out polyreaction as polycondensation catalyst, trimethyl phosphite 99.Esterification is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Keep high vacuum discharging after 185 minutes, obtain nano-titanium oxide/polyester composite, the form and aspect L value 85.52 of resin, form and aspect b value 5.18, limiting viscosity are 0.656,261.2 ℃ of fusing points, carboxyl-content are 22mol.t
-1, glycol ether content is 1.2%.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 168.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.08%.
Embodiment 5
Carry out the inorganic/organic surface modifying of nano-titanium oxide according to embodiment 1 described method, different is, and to carry out organically-modified agents useful for same be silane coupling agent agent KH560, and consumption is 3% of a nano-titanium oxide consumption.Other processing modes are all identical with temperature of reaction.
Be dispersed in the ethylene glycol according to the nano-titanium oxide of embodiment 1 described method with modification, different is that solid content of slurry is 30%.
With the 7600g dimethyl terephthalate (DMT), 400 gram dimethyl isophthalates, 4182 gram ethylene glycol and above-mentioned nano-titanium oxide slurry 1330 grams are together in 30 liters of polyester stills of making beating back adding, use antimony glycol to be polymerization stabilizer, carry out polyreaction as polycondensation catalyst, trimethyl phosphite 99.Esterification is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Keep high vacuum discharging after 160 minutes, obtain nano-titanium oxide/polyester composite, the form and aspect L value 83.46 of resin, form and aspect b value 6.39, limiting viscosity are 0.645,263.2 ℃ of fusing points, carboxyl-content are 26mol.t
-1, glycol ether content is 1.5%.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 159.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.11%.
Embodiment 6
Carry out the inorganic/organic surface modifying of nano-titanium oxide according to embodiment 1 described method, different is, and to carry out organically-modified agents useful for same be the titanate coupling agent agent, and other processing modes are all identical with temperature of reaction.
Be dispersed in the ethylene glycol according to the nano-titanium oxide of embodiment 1 described method with modification, different is that solid content of slurry is 17.5%.
With the 8000g terephthalic acid, 5933 gram butyleneglycols and above-mentioned nano-titanium oxide slurry 1220 grams together in 30 liters of polyester stills of making beating back adding, use tetrabutyl titanate to be polymerization stabilizer as polycondensation catalyst, trimethyl phosphite 99, carry out polyreaction.Esterification is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Keep high vacuum discharging after 150 minutes, obtain nano-titanium oxide/polyester composite, the form and aspect L value 86.78 of resin, form and aspect b value 7.08, limiting viscosity are 1.06,219.2 ℃ of fusing points.
With above-mentioned nano-titanium oxide/polyester composite resin 80 ℃ of dryings after 12 hours in vacuum drying oven, behind the injection molding standard testing batten, the tensile strength of sample is 58MPa, notched Izod impact strength is 5.8KJ/M2, dimension card modification temperature is 175 ℃, after 1000 hours, the every mechanical properties decrease of material is less than 5% through uviolizing for sample, and material b value is 8.23.
Embodiment 7
According to embodiment 1 described method, different is in polymerization process, except original position adds nano-titanium oxide, chemical fibre of titanium dioxide 28 grams of using as the polyester delustring that also added mean particle size and be 300 nanometers (account for 0.3% of weight polyester, mass percent), behind the in-situ polymerization, obtain nano-titanium oxide/delustring polyester composite.The form and aspect L value 88.97 of resin, form and aspect b value 3.78, limiting viscosity are 0.686,261.1 ℃ of fusing points, carboxyl-content are 26mol.t
-1, glycol ether content is 1.0%.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 69.
With above-mentioned nano-titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.09%.
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