CN1990530A - Nucleating agent of polytrimethylene terephthalate and injection moulding method - Google Patents
Nucleating agent of polytrimethylene terephthalate and injection moulding method Download PDFInfo
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- CN1990530A CN1990530A CN 200510137545 CN200510137545A CN1990530A CN 1990530 A CN1990530 A CN 1990530A CN 200510137545 CN200510137545 CN 200510137545 CN 200510137545 A CN200510137545 A CN 200510137545A CN 1990530 A CN1990530 A CN 1990530A
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- polyethylene terephthalate
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Abstract
The invention relates to nucleating agent used by Poly (ethylene terephathalate), and the injection shaping by using said nucleating agent. Said nucleating agent comprises silicon dioxide powder and dual (2- hydroxy ethyl) phthalic acid estersgrafted on the surface of said powder. The nucleating agent speeds up the crystallization rate and enables the shaping through injection.
Description
Technical field
The present invention relates to polyethylene terephthalate, particularly the nucleator and the injection moulding method of this polymkeric substance use.
Background technology
In the Materials science in modern age, materials such as polymer and metal, alloy, pottery are important development branch, and wherein complicated with high molecular technology.Influence the polymolecularity qualitative factor from characteristics such as the most basic monomeric species, the polymerization degree, until cross-linked state between monomeric arrangement mode, polymkeric substance or the like in the multipolymer all influences physical propertiess such as high molecular viscosity, degree of crystallinity, fusing point.These character will determine high molecular application and molding mode.Change the method for these character except the ratio of polymkeric substance and initiator, temperature, pressure and other parameters, adding nucleator (nucleating agent), to impel polymer crystallization also be quite common means.
The low price of polyethylene terephthalate (polyethylene terephthalate is hereinafter to be referred as PET), but the speed of its pyritous molten state crystallisation by cooling is slow, can't satisfy the required moulding in short-term of injection molding (short cycle).If the then too easily cracking (about 60-70 ℃) of product that forms in the mode of low temperature moulding.The improvement method comprises Chi at Jun.9, and 1981 in US 4,272, and 475 is disclosed, and the temperature of control reaction cylinder, the temperature of nozzle, the time and the pressure of injection are to obtain injection molding product.But its molecular weight of product that this injection moulding forms is all low, can only be used in the scope of fibre-grade or bottle, is difficult to apply to engineering level plastics.It is extremely slow in the pyritous crystallization velocity that this all problem all comes from high-molecular weight PET, higher die temperature must be arranged, fusion PET is provided bigger crystallization motivating force, therefore cooling system must be the oil bath system, water-bath system not as expensive polybutylene terephthalate (poly butylenes terephthalate is hereinafter to be referred as PBT).The oil bath system is than the cost height of water-bath system, and easily produces the engineering safety problem.
Therefore, as US 4,451,606 disclosed organic nucleating agents, for the multipolymer of utilization Sulfates, poly terephthalic acid alkyl diester (mainly being PBT) and PET as organic nucleating agent.The compatible preferable of organic nucleating agent and PET obtains average nucleating effect, but can cause the PET molecular rupture, and (280-300 ℃) can lose efficacy because of disproportionation reaction (disproportionation) or scission reaction when high temperature process.
For improving the problem of organic nucleating agent, existing many documents increase the crystallization rate of PET with inorganic nucleator.As the disclosed inorganic nucleator of US5886088, comprise the particulate or the powder of following substances: talcum (talc); mica (mica); wollastonite (wollastonite); clay (clay); kaolin (kaolin); diatomite (diatomaceous earth); wilkinite (bentonite); montmorillonite (montmorillonite); hydrotalcite (hydrotalcite); lime carbonate (calcium carbonate); titanium oxide (titanium oxide); potassium titanate (potassiumtitanate); asbestos (asbestos); barium sulphide (barium sulfide).The benefit of inorganic nucleator comprises low price, and chemical property is stable, can be used for high temperature, but and the tiny refinement geode of size particle diameter, and improve PET dimensional stability and mechanical properties.But when being high temperature, shortcoming is easy to because surface-area is big, with the few and aggegation of surface coordination.Inorganic nucleator after the aggegation can't homodisperse, will cause polymer nucleation inequality, makes the physical properties variation on the contrary.
Summary of the invention
The objective of the invention is to that (polyethylene terephthalate is PET) under the prerequisite of production process, with the even PET that is scattered in of nucleator as why not influencing existing polyethylene terephthalate.For reaching above-mentioned purpose, the invention provides a kind of inorganic/organic reaction oligomers nucleator, utilize original position (in-situ) polymeric method to reach homodisperse effect.Nucleator of the present invention can overcome the easy agglutinative phenomenon of inorganic nanometer powder, and then improves crystallization rate, mechanical properties and the thermotolerance of PET.Because nucleator of the present invention can significantly improve the crystallization rate of PET, shorten the injection molding time (short cycle), can replace the many polybutylene terephthalates of expensive raw material price (polybutyleneterephthalate, PBT), as the engineering plastics raw material of injection stage.
The invention provides a kind of nucleator of polyethylene terephthalate, comprise silicon-dioxide powdery, and the oligopolymer of two (2-hydroxyethyl) terephthalate grafts on the silicon dioxide powder surface, its structure is as follows:
Wherein n is the positive integer greater than 1.
The present invention also provides a kind of injection moulding method of polyethylene terephthalate, comprises with terephthalic acid, ethylene glycol, silicon dioxide nano powder carrying out esterification to form two (2-hydroxyethyl) terephthalate monomers and above-mentioned nucleator.Two (2-hydroxyethyl) terephthalate monomer carries out polyreaction, forms polyethylene terephthalate, and wherein two (2-hydroxyethyl) terephthalic acid ester oligomers of polyethylene terephthalate and this nucleator carry out home position polymerization reaction.With forcing machine additive is sneaked into after this polyethylene terephthalate granulation forming a plurality of mangcorns, inject the mold cools down moulding with injector after with these mangcorn hot melts and obtain finished product.
Embodiment
The invention provides a kind of inorganic/organic polyethylene terephthalate (hereinafter to be referred as PET) nucleator.This kind nucleator is that the silicon-dioxide (15-25 nanometer) that utilizes nano-scale carries out surface modification, with two (2-hydroxyethyl) terephthalate (bis (2-hydroxyethyl) terephthalate, hereinafter to be referred as BHET) oligopolymer graft on the silicon dioxide powder surface, forming particle diameter is the nucleator of 55-65 nanometer, and its structure is as follows:
N is the positive integer greater than 1, preferably between 2-15.
The oligopolymer of two (2-hydroxyethyl) terephthalate grafts on outnumber one of silicon dioxide powder surface, can effectively increase the steric hindrance of nucleator, increases the dispersive effect.Therefore on the other hand, the BHET oligopolymer is exactly the reaction monomers of PET originally, can not influence existing production process, more can be when high temperature cracking or carry out disproportionation reaction and influence quality of finished.
The present invention also provides a kind of injection moulding method of polyethylene terephthalate, comprises with terephthalic acid, ethylene glycol, silicon dioxide nano powder carrying out esterification to form two (2-hydroxyethyl) terephthalate monomers and above-mentioned nucleator.Two (2-hydroxyethyl) terephthalate monomer carries out polyreaction, form polyethylene terephthalate, wherein two (2-hydroxyethyl) terephthalic acid ester oligomers of polyethylene terephthalate and this nucleator carry out original position (in-situ) polyreaction.Additive is sneaked into (blending) this polyethylene terephthalate granulation (pellet afterwards with forcing machine, tablet, or chip), injects the mold cools down moulding with injector (eniect molding) after with these mangcorn hot melts and obtain finished product forming a plurality of mangcorns.General additive comprises chain propagation agent (Chainextender), solid-state polymerization promotor (solid-stating accelerators), impact modifier (impact modifiers), crystallization auxiliary (nucleation promoters), hydrolysis-resisting agent (anti-hydrolysis additives), reinforcer (reinforcements), fire retardant (flameretardants), or nucleator (nuacting agent, additive of the present invention does not comprise nucleator, because of nucleator has been connected on the molecular backbone chain when this experiment is synthetic), its addition is different on demand and change and differ.The cooling system of mould can change oil bath into by used water-bath in the known PET processing procedure, can reduce cost, and reduce the engineering safety accident.The cooling time that lower cooling temperature meaning is promptly short, and reduce machine injection molding cycling time (cycle time).The temperature of esterification is between 150-200 ℃, and the temperature of polyreaction is between 250-300 ℃.The molecular weight of above-mentioned finished product is 15000～20000, is preferably about 18000.The crystallisation by cooling temperature of the finished product of polyethylene terephthalate is greater than 200 ℃.The finished product of polyethylene terephthalate is below 190 ℃, and required time of hypocrystalline was less than one minute.In the process of polycondensation, the reactive oligomers in the nucleator of the present invention and other monomer in-situ polymerization, and nano silicon is dispersed in the PET matrix.Because the BHET molecular weight is along with reaction is constantly grown up, can have better thermostability, do not have general small molecules organic nucleating agent non-refractory and the shortcoming that ruptures, and give the silicon dioxide powder surface bigger steric hindrance, increase the dispersive effect.
Except the above-mentioned practice, after the present invention also can form the pure material of PET earlier, add nucleator of the present invention and other additive again and sneak into granulating behind the pure material of PET, again with mangcorn injection molding.
Prior art all adopts high temperature 280-300 ℃ with behind the PET hot melt, adds nucleator again, mixes granulating by mechanical force.Yet the PET that this kind method forms is very easy to thermal destruction (thermal degradation) or thermooxidative degradation (thermaloxidative degradation) when high temperature process, and organic nucleating agent lost efficacy easily during high temperature, the easy aggegation of inorganic nucleator.Nucleator of the present invention is formed at Esterification Stage, with the reaction monomers in-situ polymerization, can not produce the problem that known processing procedure and nucleator cause.
Its crystallographic property of polymkeric substance of using nucleator of the present invention is similar with expensive PBT, so finished product can be applicable to part, the electrical/electronic part of the vehicles such as engineering level plastics such as automobile.And nucleator of the present invention can increase wear resistance and the mechanical properties of PET because the composition of silicon-dioxide is arranged, and can replace products such as nylon industry fiber such as fishing line, fishnet, tire cord on using.
For making the clearer feature of the present invention of those skilled in the art, exemplify following preferred embodiment.
Preferred embodiment
Embodiment 1
Get ethylene glycol (63g, 1mol), silicon-dioxide (1.2g, 19.9mmol), (166g is 1mol) in back pressure 3kg/cm for terephthalic acid
2Nitrogen under be heated to 180-200 ℃ and distillate water.Esterification finishes after about 2.5 hours, be warming up to 280 ℃ and vacuumize (less than 60mmHg) after carry out polycondensation reaction, to obtain nucleator.The particle diameter of this nucleator is 59.8 nanometers.And heat analysis data there is no the pyrolysated phenomenon after being presented at and being heated to 300 ℃, has good thermostability.Above-mentioned reaction formula can be referring to following formula:
Embodiment 2
Get two (2-hydroxyethyl) terephthalic acid ester oligomer (50g, 0.2mol), silicon-dioxide powdery (5g, 0.08mol) heating (temperature is decided on the oligopolymer polymerization degree) extremely fusing in about 1.5 hours, then be warming up to 280 ℃ and vacuumize (less than 60mmHg) after carry out polycondensation reaction, obtain nucleator.The character similar embodiment 1 described nucleator of this nucleator, its reaction formula as shown in the formula:
Embodiment 3
Above-mentioned nucleator, the terephthalic acid (166g) of getting ethylene glycol (63g), different ratios carry out polyreaction to obtain PET (molecular weight is 18000).The nucleator that will have different ratios with the character comparison of pure PET, PBT, can get the data of following table:
| PBT | PET | The PET/ nucleator | The PET/ nucleator | The PET/ nucleator | The PET/ nucleator | |
| SiO 2(weight %) | 0 | 0 | 0.25 | 0.5 | 1 | 3 |
| Tg(℃) | 45 | 76.9 | 74.4 | 76.5 | 77.7 | 76.1 |
| Tm(℃) | 220 | 249.2 | 250.1 | 254.3 | 253.1 | 259.3 |
| Tcc(℃) | 174.8 | 167.3 | 182.5 | 205 | 182.0 | 180.6 |
| Degree of crystallinity (%) | 8.5 | 1.6 | 2.3 | 8.5 | 4.3 | 5.9 |
Can find significantly by last table, add the similar PBT of its character of PET of nucleator.Except glass transition temperature Tg, the injection molding parameters of influence such as crystal melting temperature (Tm), crystallisation by cooling temperature (Tcc), degree of crystallinity all are better than not adding the PET of nucleator.In addition, be example to add 0.5% nucleator, in the time of 190 ℃, crystallization semi-period time (t
1/2) be contracted to 0.87 minute from 2.55 minutes of the PET that does not originally add nucleator.This crystallization time that significantly reduces makes injection molding finished product have the character of similar PBT, but needn't be as the raw material expensive (the PET cost of material is half of PBT approximately) of PBT.
Though it is above-mentioned open that the present invention has carried out with several preferred embodiments; yet it is not in order to limit the present invention; any those skilled in the art; do not break away from the spirit and scope of the present invention; can change arbitrarily and retouching, so protection scope of the present invention should be as the criterion with claim institute restricted portion.
Claims (15)
1. the nucleator of a polyethylene terephthalate comprises:
Silicon-dioxide powdery; And
The oligopolymer of two (2-hydroxyethyl) terephthalate grafts on this silicon dioxide powder surface;
Its structure is as follows:
Wherein n is the positive integer greater than 1.
2. the nucleator of the polyethylene terephthalate of claim 1, its polymerization degree n=2-15.
3. the nucleator of the polyethylene terephthalate of claim 1, wherein the particle diameter of this silicon-dioxide powdery is between the 15-25 nanometer.
4. the nucleator of the polyethylene terephthalate of claim 1, its particle diameter is between the 55-65 nanometer.
5. the injection moulding method of a polyethylene terephthalate comprises:
Carry out esterification to form the nucleator of two (2-hydroxyethyl) terephthalate monomers and claim 1 with terephthalic acid, ethylene glycol, silicon dioxide nano powder;
This pair (2-hydroxyethyl) terephthalate monomer carries out polyreaction, form polyethylene terephthalate, wherein two (2-hydroxyethyl) terephthalic acid ester oligomers of this polyethylene terephthalate and this nucleator carry out home position polymerization reaction;
With forcing machine additive is sneaked into the granulation afterwards of this polyethylene terephthalate to form a plurality of mangcorns; And
Inject the mold cools down moulding after with these mangcorn hot melts with injector and obtain finished product.
6. the injection moulding method of the polyethylene terephthalate of claim 5, wherein this additive comprises chain propagation agent, solid-state polymerization promotor, impact modifier, crystallization auxiliary, hydrolysis-resisting agent, reinforcer, fire retardant.
7. the injection moulding method of the polyethylene terephthalate of claim 5, the device that wherein carries out this mold cools down is the water-bath system.
8. the injection moulding method of the polyethylene terephthalate of claim 5, wherein this finished product is engineering level plastics.
9. the injection moulding method of the polyethylene terephthalate of claim 5, wherein the molecular weight of this finished product is between 15000-20000.
10. the injection moulding method of the polyethylene terephthalate of claim 5, wherein the molecular weight of this finished product is preferably about 18000.
11. the injection moulding method of the polyethylene terephthalate of claim 5, wherein the temperature of this esterification is lower than the temperature of this polyreaction.
12. the injection moulding method of the polyethylene terephthalate of claim 11, wherein the temperature of this esterification is between 150-200 ℃.
13. the injection moulding method of the polyethylene terephthalate of claim 11, wherein the temperature of this polyreaction is between 250-300 ℃.
14. the injection moulding method of the polyethylene terephthalate of claim 5, wherein the crystallisation by cooling temperature of this finished product is greater than 200 ℃.
15. the injection moulding method of the polyethylene terephthalate of claim 5, wherein this finished product is below 190 ℃, and required time of its hypocrystalline was less than 1 minute.
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| CNB2005101375458A CN100465216C (en) | 2005-12-30 | 2005-12-30 | Nucleating agent of polytrimethylene terephthalate and injection moulding method |
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| CNB2005101375458A CN100465216C (en) | 2005-12-30 | 2005-12-30 | Nucleating agent of polytrimethylene terephthalate and injection moulding method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110406059A (en) * | 2019-07-12 | 2019-11-05 | 广东科龙模具有限公司 | A kind of Shooting Technique of recycled PET material crystallisation by cooling |
| CN111995739A (en) * | 2020-07-30 | 2020-11-27 | 浙江恒澜科技有限公司 | Low-melting-point copolyester and preparation method thereof |
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| ES2264256T3 (en) * | 1998-03-20 | 2006-12-16 | Dow Global Technologies Inc. | USE OF A THERMOFUSIBLE ADHESIVE OF A POLYMER COMPOSITE MATERIAL THAT INCLUDES A POLYESTER WITH HYDROXY FUNCTIONALITY AND AN INORGANIC LOAD. |
| CN1094497C (en) * | 1999-01-19 | 2002-11-20 | 中山大学 | Nanometre inorganic particle toughened reinforced plastics and preparation method thereof |
| CN1260293C (en) * | 2003-08-01 | 2006-06-21 | 上海普利特复合材料有限公司 | Method for preparing chemical nucleation glass fiber reinforced polyester composite material |
| CN1281695C (en) * | 2004-12-06 | 2006-10-25 | 复旦大学 | Nanometer composite polyester resin paint with high solid content and low viscosity and its prepn |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110406059A (en) * | 2019-07-12 | 2019-11-05 | 广东科龙模具有限公司 | A kind of Shooting Technique of recycled PET material crystallisation by cooling |
| CN111995739A (en) * | 2020-07-30 | 2020-11-27 | 浙江恒澜科技有限公司 | Low-melting-point copolyester and preparation method thereof |
| CN111995739B (en) * | 2020-07-30 | 2023-02-17 | 浙江恒逸石化研究院有限公司 | Low-melting-point copolyester and preparation method thereof |
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