CN103642012A - Method for preparing high-flow and high-modulus polybutylene terephthalate - Google Patents
Method for preparing high-flow and high-modulus polybutylene terephthalate Download PDFInfo
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- CN103642012A CN103642012A CN201310549394.1A CN201310549394A CN103642012A CN 103642012 A CN103642012 A CN 103642012A CN 201310549394 A CN201310549394 A CN 201310549394A CN 103642012 A CN103642012 A CN 103642012A
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Abstract
The invention discloses a method for preparing high-flow and high-modulus polybutylene telephthalate, belonging to a technology for preparing a heat-shrinkable resin. The method for preparing the high-flow and high-modulus polybutylene telephthalate comprises: selecting proper auxiliary agent kinds and usage dosages; and reasonably determining a technology process of adding the auxiliary agent into a main raw material to generate a high-flow and high-modulus polybutylene telephthalate polymer. Finally, the polymer should satisfy the following indexes: intrinsic viscosity being 1.0-1.2dl/g, carboxyl not more than 30 mol/L, tensile strength not less than 50MPa, fracture elongation not less than 250%, and elastic modulus not less than 2400MPa. A high-flow and high-modulus polybutylene telephthalate product prepared by the technology raises fluidity, simultaneously maintains mechanical properties of the product, and raises the elastic modulus of the product. The product satisfies processing requirements on products with various complex shapes.
Description
Technical field: the technology of preparing that the present invention relates to a kind of red shortness's resin.
Background technology: polybutylene terephthalate (PBT) is a kind of engineering plastics of excellent combination property, adds glass and some auxiliary agents to improve the mechanical property of PBT before use, but adds glass and auxiliary agent can make its mobility variation.And the shape need PBT blend that various product becomes increasingly complex has good flowing property, particularly thin wall parts and complicated accurate product, require can be full of fast die cavity in the course of processing.After PBT melting, there is higher viscosity, in the course of processing, the superpolymer of melting is when by runners such as narrow slit, cast gates, polymkeric substance can produce friction with processor surface, these frictions reduce fluidity of molten, serious friction can make film surface become coarse, lacks gloss or occurs crackle.Need to add the auxiliary agent that improves oilness, minimizing friction, reduces Interface Adhesion performance for this reason.The performance that how to guarantee not change existing product when improving PBT mobility and Young's modulus is the problem that needs research and probe.
Summary of the invention: the object of the invention is to design a kind ofly highly flow, high-modulus polybutylene terephthalate's preparation method, realize the target that does not change the performance of existing product when improving PBT mobility and Young's modulus.The object of the present invention is achieved like this: height flows, high-modulus polybutylene terephthalate's preparation method, comprises and select suitable auxiliary agent kind and using dosage; Rationally determine that these auxiliary agents add main raw material to generate highly to flow, the technological process of high-modulus polybutylene terephthalate polymkeric substance; Check the key index of polymkeric substance to be-and limiting viscosity is 1.0-1.2dl/g, carboxyl is≤30mol/t that tensile strength is >=50MPa that elongation at break is >=250%, Young's modulus >=2400MPa.
The selection scheme of its auxiliary agent is: lubricant accounts for the 0.5-5% of raw material weight, and cross linking agent accounts for the 0.005-0.05% of raw material weight, and catalyzer accounts for the 0.05-0.2% of raw material weight, and toning agent accounts for the 0.0006-0.003% of raw material weight.Wherein lubricant is pentaerythritol stearate; Cross linking agent is glycerine; Catalyzer is tetrabutyl titanate; Toning agent is the purple agent that food adds;
Above-mentioned auxiliary agent adds main raw material to generate high technological process mobile, high-modulus polybutylene terephthalate polymkeric substance:
1. slurry configuration terephthalic acid powder successively adds in slurry configured slot and stirs with the ratio of 1:1.4 (mol ratio) through metering system metering and liquid butyleneglycol, and cross linking agent, toning agent are added in slurry configured slot by formula ratio, with dehvery pump, send into esterifier after being mixed into uniform sizing material.
2. the slurry that esterification mixes is at esterifier interior reaction temperature 236-243 ℃, vacuum tightness 300-400mbr, residence time 100-150min; After terephthalic acid and the water outlet of butyleneglycol Reaction Separation, generate the two hydroxyl butyl esters of terephthalic acid, esterification yield can reach more than 99.6%, and the material after esterification is delivered to Prepolycondensating reactor;
3. the operational condition that the two hydroxyl butyl esters of precondensation terephthalic acid enter Prepolycondensating reactor is temperature 240-243 ℃, vacuum tightness 5-10mbr, residence time 30-60min, reaction generates low molecular polybutylene terephthalate, on prepolymer transport pipe, by formula ratio, add lubricant, enter together final minification still;
4. the disk that the poly-material coming from Prepolycondensating reactor of final minification is rotated final polycondensation reactor drives and forms the surface of rotating, be conducive to the discharge of low molecule by product, the poly-operational condition of final minification is temperature 240-250 ℃, vacuum tightness 0.5-1mbr, residence time 2-5h can obtain that qualified height flows, high-modulus polybutylene terephthalate polymeric articles.
The height of preparing by above-mentioned technique flows, high-modulus polybutylene terephthalate product has improved mobility, keeps the mechanical property of product simultaneously, has improved the Young's modulus of product.Met the processing request to all kinds of complex-shaped products.
Embodiment: be further described below in conjunction with embodiment.
Specific embodiments one, the umber in scheme is mass fraction.
By 780 parts of pure terephthalic acids, 520 parts of Isosorbide-5-Nitrae-butyleneglycols, 0.15 part of cross linking agent, 0.001 part of toning agent, drops into hollander tub and carries out slurry preparation.The slurry mixing enters esterifier together with 0.8 part of transferpump and catalyzer, 238 ℃ of esterification reaction temperatures, and vacuum tightness 340mbr, material stops 130min in esterifier, carries out esterification, and esterification yield can reach 99.7%.The two hydroxyl butyl esters (BHBT) of product terephthalic acid after esterification are sent into Prepolycondensating reactor by discharging pump.The operational condition of Prepolycondensating reactor is 240 ℃ of temperature, vacuum tightness 6mbr, reacts residence time 60min under condition.Precondensation product enters final polycondensation reactor together with 32 parts of lubricants, final polycondensation reactor operational condition is 248 ℃ of temperature, vacuum tightness 0.6mbr, residence time 4h, the height that acquisition meets polymkeric substance index flows, high-modulus polybutylene terephthalate, through pelletizing, be packaged to finished product.
Specific embodiments two
By 756 parts of pure terephthalic acids, 501 parts of BDOs, 0.20 part of cross linking agent, 0.0006 part of toning agent, drops into hollander tub and carries out slurry preparation.Slurry enters esterifier together with 0.6 part of pump and catalyzer.240 ℃ of esterification reaction temperatures, vacuum tightness 360mbr, material stops 120min in esterifier, carries out esterification, and esterification yield can reach 99.6%.The two hydroxyl butyl esters (BHBT) of esterification products terephthalic acid enter Prepolycondensating reactor, and the operational condition of Prepolycondensating reactor is 242 ℃ of temperature, vacuum tightness 5mbr, reacts residence time 50min under condition.Precondensation product enters final polycondensation reactor together with 26 parts of lubricants, and final polycondensation reactor operational condition is 246 ℃ of temperature, vacuum tightness 1mbr, residence time 3.5h.Through pelletizing, be packaged to finished product.
Claims (1)
1. high flow, high-modulus polybutylene terephthalate's preparation method, comprise and select suitable auxiliary agent kind and using dosage, rationally determine that these auxiliary agents add main raw material to generate highly to flow, high-modulus polybutylene terephthalate's technological process; The key index of polymkeric substance is-and limiting viscosity is 1.0-1.2dl/g, and carboxyl is≤30mol/t that tensile strength is >=50MPa that elongation at break is >=250%, Young's modulus >=2400MPa;
The selection scheme of its auxiliary agent is: lubricant accounts for the 0.5-5% of raw material weight, and cross linking agent accounts for the 0.005-0.05% of raw material weight, and catalyzer accounts for the 0.05-0.2% of raw material weight, and toning agent accounts for the 0.0006-0.003% of raw material weight; Wherein lubricant is pentaerythritol stearate; Cross linking agent is glycerine; Catalyzer is tetrabutyl titanate; Toning agent is the purple agent that food adds;
Above-mentioned auxiliary agent adds main raw material to generate high technological process mobile, high-modulus polybutylene terephthalate:
1. slurry configuration terephthalic acid powder successively adds in slurry configured slot and stirs with the ratio of 1:1.4 (mol ratio) through metering system metering and liquid butyleneglycol, and cross linking agent, toning agent are added in slurry configured slot by formula rate, with dehvery pump, send into esterifier after being mixed into uniform sizing material;
2. the slurry that esterification mixes is at esterifier interior reaction temperature 236-243 ℃, vacuum tightness 300-400mbr, residence time 100-150min; Terephthalic acid generates the two hydroxyl butyl esters of terephthalic acid and more high molecular oligopolymer after reflecting separated water outlet with butyleneglycol, esterification yield can reach more than 99.6%, and the material after esterification is delivered to preshrunk reactor;
3. the operational condition that the two hydroxyl butyl esters of precondensation terephthalic acid enter Prepolycondensating reactor is temperature 240-243 ℃, vacuum tightness 5-10mbr, residence time 30-60min, reaction generates low molecular polybutylene terephthalate, on prepolymer transport pipe, add lubricant, enter together final minification still;
4. the disk that the poly-material coming from Prepolycondensating reactor of final minification is rotated final polycondensation reactor drives and forms the surface of rotating, be conducive to the discharge of low molecule by product, dividing shadow condition is temperature 240-250 ℃, vacuum tightness 0.5-1mbr, residence time 2-5h can obtain that qualified height flows, high-modulus polybutylene terephthalate product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310549394.1A CN103642012A (en) | 2013-10-30 | 2013-10-30 | Method for preparing high-flow and high-modulus polybutylene terephthalate |
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| CN201310549394.1A CN103642012A (en) | 2013-10-30 | 2013-10-30 | Method for preparing high-flow and high-modulus polybutylene terephthalate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017338A (en) * | 2014-06-23 | 2014-09-03 | 华润包装材料有限公司 | Polyester slices for manufacturing vacuum blood collection tube and preparation method of polyester slices |
| CN105440604A (en) * | 2015-12-23 | 2016-03-30 | 江苏金发科技新材料有限公司 | Low surface tension PBT resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1926169A (en) * | 2004-04-01 | 2007-03-07 | 三菱化学株式会社 | Polybutylene terephthalate film and sheet and method for producing them |
| CN102477148A (en) * | 2010-11-25 | 2012-05-30 | 新疆蓝山屯河聚酯有限公司 | High-viscosity PBT resin special for optical fiber protective sleeve and production method thereof |
| CN102504217A (en) * | 2011-10-23 | 2012-06-20 | 新疆蓝山屯河聚酯有限公司 | Method for preparing special polybutylene terephthalate for high-speed spinning |
-
2013
- 2013-10-30 CN CN201310549394.1A patent/CN103642012A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1926169A (en) * | 2004-04-01 | 2007-03-07 | 三菱化学株式会社 | Polybutylene terephthalate film and sheet and method for producing them |
| CN102477148A (en) * | 2010-11-25 | 2012-05-30 | 新疆蓝山屯河聚酯有限公司 | High-viscosity PBT resin special for optical fiber protective sleeve and production method thereof |
| CN102504217A (en) * | 2011-10-23 | 2012-06-20 | 新疆蓝山屯河聚酯有限公司 | Method for preparing special polybutylene terephthalate for high-speed spinning |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017338A (en) * | 2014-06-23 | 2014-09-03 | 华润包装材料有限公司 | Polyester slices for manufacturing vacuum blood collection tube and preparation method of polyester slices |
| CN105440604A (en) * | 2015-12-23 | 2016-03-30 | 江苏金发科技新材料有限公司 | Low surface tension PBT resin |
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Application publication date: 20140319 |