CN1202169C - Thermoplastic resin composition and product thereof - Google Patents
Thermoplastic resin composition and product thereof Download PDFInfo
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- CN1202169C CN1202169C CN 03112194 CN03112194A CN1202169C CN 1202169 C CN1202169 C CN 1202169C CN 03112194 CN03112194 CN 03112194 CN 03112194 A CN03112194 A CN 03112194A CN 1202169 C CN1202169 C CN 1202169C
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Abstract
The present invention relates to a thermoplastic polyester group resin composition and a manufactured product thereof, more specifically the technical fields of a polyterephthalic acid propylene glycol ester type resin composition and a manufactured product thereof. The composition of the present invention comprises the polyterephthalic acid propylene glycol ester type resin or the polyterephthalic acid propylene glycol ester type resin with doped other kinds of resin, a phenol-4-sulfonic acid alkali metal salt crystallization nucleus increasing agent or a composite crystallization nucleus increasing agent containing Phenol-4-sulfonic acid alkali metal salt, and reinforcing fibers. The resin composition of the present invention can be used for manufacturing various structural members, such as electronic products, electric products, instruments, meters, mechanical appliances, automobiles, etc., for manufacturing plastic films for the purposes of packaging, etc., for manufacturing tubular products, such as electric wire sleeve tubes, optical fiber loose sleeve tubes, etc., and for manufacturing engineering plastic raw materials of other manufactured products. The present invention fundamentally solves the serious problem of slow crystallization speed of the terephthalic acid propylene glycol ester type resin when the terephthalic acid propylene glycol ester type resin is used as an industrial plastic material.
Description
(1) technical field
The present invention relates to a kind of thermoplastically polyester family tree oil/fat composition and goods thereof, be specifically related to polypropylene terephthalate's resin combination and product technique field thereof.
(2) technical background
Poly(Trimethylene Terephthalate) (English name poly (trimethylene terephthalate), also claim poly (propylene terephthalate), abbreviation PTT or PPT are designated hereinafter simply as PTT) be the polyester family macromolecular material of industrial new appearance in recent years.Though the name of PTT just is being familiar with by people a long time ago, because the early stage synthetic high molecular starting material 1 of PTT, ammediol (1, costing an arm and a leg 3-propanediol), the source of PTT macromolecular material only is confined to small-scale the synthesizing laboratory in.Therefore, early stage people research that the PTT macromolecular material is carried out is confined to basic sphere of learning.In recent years people have had breakthrough at starting material 1 on the industrial preparative method of ammediol, and the hope of cheap scale operation PTT macromolecular material is come true.Owing to the PTT polymer is being subjected to presenting very good recovery characteristics and good characteristics such as chemical resistance when stress is out of shape, the PTT material just little by little is being used in the fibril materials of producing high-grade clothing, carpet etc.Recently, people are beginning to explore the possibility of PTT material as the engineering plastic materials of the material of manufacturing film and various Industrial products, people's livelihood end-use again.
Yet as a kind of novel engineering plastic materials, when resin was compared, the crystallization speed of PTT resin was very slow with present polybutylene terephthalate that generally adopted by engineering plastic materials market, that belong to polyester family (being called for short PBT).The report of relevant this respect, can consult H.H. looks into, the crystallization kinetics of Poly(Trimethylene Terephthalate), macromolecule engineering and science, 41,2000, P308 (H.H.Chuah, Crystallization Kinetics ofPoly (trimethylene terephthalate), Polymer Engineering ﹠amp; Science, 41,2000, P308).The speed of crystallization slowly of PTT resin can not be suitable for process for processing modes such as low temperature moulding, rapid shaping, is a serious defective for the PTT resin as the application of engineering plastic materials aspect.
Because of the well-known polyethylene terephthalate of the name of fiber terylene (English name poly (ethyleneterephthalate) is designated hereinafter simply as PET) resin, belong to polyester family macromolecular material equally.The past people are aspect the crystallization speed that improves improvement PET resin, once did a large amount of work, comprised the trial investigation that increases the nuclear effect as crystallization the organic compound that adds inorganic micro powder, sodium stearate, Sodium Benzoate, o-halogenated benzoic acid sodium, ethylene-methacrylic acid copolymer sodium salt and so on such as talcum etc.Open report is seen patent documentation GB 2015014A; US 4425470.In general, inorganic micro powders such as interpolation talcum are less abundant for the effect of the crystallization speed that promotes the PET resin, and add low-molecular-weight basic metal organic compound, Sodium Benzoate etc. for example, though it is effective to a certain extent for the crystallization speed that promotes the PET resin, but can cause the thermolysis of PET resin under molten state, the reduction of molecular weight simultaneously, plastic ties ruptures when causing extrusion molding process for processing resin combination, the moulding product are chipping during forming process, a series of problem such as the moulding product mechanical property that obtains is bad.Add the high-molecular weight alkali metal ionomers, the an alkali metal salt of ethylene-methacrylic acid copolymer for example, because the reasons such as ion bridge formation between the molecular bridge between the remaining carboxyl of ionomer and the PET C-terminal, the carboxyl terminal alkalimetal ion of ionomer and the PET terminal hydroxyl, cause the raising significantly of melt viscosity, the poor flow quality when causing forming process of resin.Although people are in all effort and the cheap prices of raw and semifnished materials advantage that PET resin itself has of making aspect the raising improvement PET resin crystallization speed, but, and finally fail to be accepted extensively by engineering plastic materials market because the crystallization speed of PET resin combination does not reach the index that can be used to carry out typical temperature injection molding processing.
In general, if the crystallization velocity ratio of a kind of hypocrystalline castable resin composition hot in nature is slower, with this resin combination is that raw material is when carrying out the moulding process for processing and preparing the moulding product, have the generation of the release bad phenomenon of moulding product mould, the moulding product that obtain are not high enough because of degree of crystallization, shortcomings such as mechanical strength is not high, resistance toheat difference; This resin combination can not be fit to the mode of production of rapid shaping processing, influences production efficiency; When running into higher temperature, crystallization takes place in resin combination moulding product again, causes the variation of size, shape.In addition, because it is different with the inner temperature history that is experienced during moulding with the contacted upper layer of mould, the degree of crystallization of the various piece of the moulding product that obtain is also variant, shrinkage coefficient is different in different directions, cause the incongruent problem of physical size, shape and design requirements of moulding product, be not easy to obtain the qualified product of high-quality.The crystallization speed of utilizing the hot castable resin of hemicrystalline under the condition of high temperature is characteristics faster, forming mould is arranged at carries out forming process under the hot conditions, though also can be used as the degree of crystallinity that improves the moulding product to a certain extent and improve inhomogeneity a kind of method that degree of crystallinity distributes, but, improve the forming mould temperature and carry out high-temperature molding, not only need special intensification equipment, increase investment burden, but also can cause the problem that shaping cycle prolongs, production efficiency reduces, certain limitation is arranged.This shows when the PTT resin is utilized as engineering plastic materials, how to improve the degree of crystallinity of PTT synthetic resin and improve the homogeneity that degree of crystallinity distributes, after all, improving the crystallization speed of improving the PTT resin is important key.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of Thermoplastic resin combination of polypropylene terephthalate and its formed pieces, the slow-paced major defect of crystallization when fundamentally solving propylene glycol ester terephthalate's resinoid as the industrial plastic material.
Technical scheme of the present invention is as follows:
Thermoplastic resin composite of the present invention comprises, all is weight percentage:
(a) PTT resinoid or mix the PTT resinoid of other resins, surplus,
(b) p-hydroxybenzenyl sulfonate an alkali metal salt crystallization increases the nuclear agent, or the composite junction crystallization that contains the p-hydroxybenzenyl sulfonate an alkali metal salt increases the nuclear agent, and 0.005%～6%,
(c) fortifying fibre, 0～65%.
Per-cent in the above-mentioned thermoplastic resin composite is meant each component shared weight percent in thermoplastic resin composite.
(a) is though composition is main resinous principle with the PTT resinoid in the above-mentioned resin combination, but also can be according to the needs of material property, add various types of other resinous principles, such as the PET resin, the PBT resin, polycarbonate (PC) resin, nylon 6 (PA6) resin, nylon 66 (PA66) resin, high impact-resistant polystyrene (HIPS) resin, the multipolymer of acrylonitrile and butadiene (AS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, polymethylmethacrylate (PMMA) resins etc., other resinous principles that mix account for below 50% of (a) component.
Under 30 ℃ of conditions of temperature, with weight ratio is that 1: 1 methyl chloride and trifluoracetic acid are when measuring, intrinsic viscosity is that the PTT resinoid of 0.4dl/g～1.6dl/g scope relatively helps manufacturing thermoplastic resin composition and its products of the present invention, and the PTT resinoid of 0.6dl/g～1.3dl/g scope is more good.When intrinsic viscosity is lower than 0.4dl/g,, can not get the favorable mechanical mechanical property because molecular chain length is too short.When intrinsic viscosity was higher than 1.6dl/g, melt flow property was too poor, and processability is bad.
Needn't specific in addition restriction to PTT resinoid manufacture method, common manufacture method is such as melt phase polycondensation, and solid phase polycondensation or the former two's combination etc. can realize.
Described (a) PTT resinoid is to substitute mixture and 1 with terephthalic acid (PTA) or its part, the polymkeric substance that the polycondensation that ammediol is a main component by direct condensation (direct esterification method) obtains, perhaps substitute mixture and 1, the polymkeric substance that the polycondensation that ammediol is a main component by transesterify (indirect esterification process) obtains with dimethyl terephthalate (DMT) (DMT) or its part.
In the above-mentioned polycondensation, PTA can carry out part with other dicarboxylic acid and substitute, and DMT can carry out part with other diester class and substitute; 1, ammediol can carry out part and substitute with other the raw material of glycols.
The dicarboxylic acid that substitutes PTA in order to part has: phthalic acid, m-phthalic acid, naphthalene dicarboxylic acids, hexanodioic acid etc.Substituting DMT diester class in order to part has: to the phenylene-diacetic acid dimethyl ester, and to benzene dipropionic acid dimethyl ester, dimethyl phthalate, dimethyl isophthalate, naphthalene dicarboxylic acids dimethyl ester, dimethyl adipate etc.Substitute 1 in order to part, the glycols of ammediol has: the carbon number is the aliphatics Huo person Ring aliphatic diol class of 2～20 scopes etc., specifically, and such as ethylene glycol, 1,4-butyleneglycol, 1,3 butylene glycol, 1,2-propylene glycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,4-cyclohexanediol etc.For PTA, DMT, 1, the alternative amount of ammediol should be controlled at the scope of mol ratio below 30%, and comparatively ideal situation is to be controlled at the scope of mol ratio below 10%.Too much replacement might cause the PTT resin to lose original characteristic.
Above-mentioned (b) component p-hydroxybenzenyl sulfonate an alkali metal salt is a class because of the compound that the hydroxyl in the p-hydroxybenzenyl sulfonate and sulfonic group have at least a part to obtain through the neutralization reaction with alkalimetal ion.As for the hydroxyl of p-hydroxybenzenyl sulfonate and sulfonic group by alkalimetal ion neutral degree, with the p-hydroxybenzenyl sulfonate an alkali metal salt that accounts for hydroxyl and sulfonic group total amount 30% mol ratio～100% mol ratio is good, accounts for the better effects if that hydroxyl and sulfonic group total amount are the p-hydroxybenzenyl sulfonate an alkali metal salt of 70% mol ratio～100% mol ratio.Increase the nuclear agent as crystallization, the hydroxyl of p-hydroxybenzenyl sulfonate and sulfonic both sides are simultaneously by ideal with the effect of the p-hydroxybenzenyl sulfonate an alkali metal salt of crossing in the alkalimetal ion.
Said basic metal is meant lithium, sodium, potassium etc., increases the nuclear agent as crystallization, the best results of the p-hydroxy benzenyl sulfonate sodium salt that the sodium ion neutralization obtains.
As for (b) component shared part by weight in resin combination, can between 0.005%～6% scope, suitably regulate according to the crystallization speed index of the resin combination of the resinoid initial intrinsic viscosity of employed PTT, needs preparation and to the requirement of the intrinsic viscosity of the PTT resinoid composition in the resin combination.If (b) component p-hydroxybenzenyl sulfonate an alkali metal salt composition is lower than 0.005% weight percent, may be not really abundant for the effect that promotes crystallization speed, might not reach the purpose that improves the crystallization speed of improving the PTT based resin composition.If (b) component p-hydroxybenzenyl sulfonate an alkali metal salt composition surpass 3% or the composite junction crystallization increase the nuclear agent and surpass 6% weight percent, might cause material cost to take irrational rising, and the superperformance of resin combination itself can be damaged because of the reduction of PTT resinoid molecular weight to a certain extent.(b) percentage of the shared resin combination gross weight of component is that the over-all properties of 0.01%～3% resin combination is relatively good, also practical.
The p-hydroxybenzenyl sulfonate an alkali metal salt be the composite junction crystallization of composition increase nuclear agent be meant, one or more of organic compound an alkali metal salts such as inorganic micro powder, P-hydroxybenzoic acid sodium salt, ethylene-methacrylic acid copolymer sodium ion cross-linked polymer salt such as selection interpolation talcum powder increase the nuclear agent as second crystallization, with p-hydroxybenzenyl sulfonate an alkali metal salt and usefulness, when reaching the requirement of the crystallization speed that satisfy to promote the PTT based resin composition, to a certain extent the viscosity of resin combination etc. is regulated.Increase in the nuclear agent p-hydroxybenzenyl sulfonate an alkali metal salt at crystallization, one or more of organic compound an alkali metal salts such as selection interpolation talcum powder inorganic micro powder, P-hydroxybenzoic acid an alkali metal salt, ethylene-methacrylic acid copolymer alkali metal ionomers salt increase the nuclear agent as second crystallization, and the alkalimetal ion of p-hydroxybenzenyl sulfonate an alkali metal salt accounts for the composite junction crystallization and increases more than 30% mol ratio of examining alkalimetal ion total amount in the agent.
Above-mentioned (c) component fortifying fibre, be used for the fibrous packing material of mechanics of machinery character of reinforced resin composition moulding product, can be glass fibre, carbon fiber, steel fiber etc., account for the weight percent 0～65% of resin combination, practical scope be present between 10～50%.(c) the ingredients constitute weight percent surpasses 65% resin combination, and extrusion molding and moulding be difficulty relatively.
In general, glass fibre is both economical, and carbon fiber helps the lightweight of moulding product, and the static that steel fiber helps the moulding product prevents function.As the reinforcing glass filamentary material, can be E glass, C glass, S glass, S-2 glass etc.Because it is less that the E glass fibre contains alkaline components, thereby electrical insulation properties is good, especially is suitable as the strongthener of PTT resin.Though the diameter to glass fibre requires to add special restriction, diameter helps the manufacturing production of fortifying fibre resin combination and moulding product thereof at the glass fibre of 1 μ m～100 mu m ranges, the glass fibre of 2 μ m～50 mu m ranges is more practical, the glass fibre of 3 μ m～30 mu m ranges is good, and the glass fibre of 5 μ m～20 mu m ranges is even more ideal.Diameter is not easy to make less than the glass fibre of 1 μ m, and the cost cost is higher.Diameter has the possibility that causes that tensile strength weakens greater than the glass fibre of 100 μ m.In the present invention, though the length to glass fibre needn't be limited especially, but in fact, mean length is that the glass fibre of 0.05mm～20mm scope is practical, and the 1mm～glass fibre of 10mm scope helps the manufacturing of fortifying fibre resin combination and moulding product thereof.The glass fibre that mean length is shorter than 0.05mm may be not really abundant to the reinforced effects of resin combination moulding product.Mean length is greater than the glass fibre of 20mm, and resin combination bigger difficulty occurs possibly at mix extrusion molding and formative stage.
As strengthening packing material, effective with the fiber reinforcement of handling through surface treatment agent.Through after the processing of surface treatment agent, can carry out firm combining between resin and fiber, stress can successfully be delivered to fiber from the PTT resinoid, and then reaches the reinforced effects of fiber.Kind to surface treatment agent needn't be limited especially, can use for example chlorosilane compounds such as trieline silane, ethylene methacrylic dichlorosilane, the compound of alcoxyl such as vinyltrimethoxy silane, vinyltriethoxysilane base class, the compound of epoxy radicals silicone hydride class, the polymkeric substance of acroleic acid resin class etc.
Through and bringing the glass fibre utilization convenience that agent was handled together, also play the effect that prevents glass fibre damage itself simultaneously.Needn't be limited especially the kind of bringing agent together, can be used for example vinyl acetate resin, ethylene-vinyl acetate copolymer, acrylic resin, Resins, epoxy, polyurethane resin, the resin emulsion of vibrin etc. etc.
Resin combination among the present invention comprises that also other are of value to the additive that improves various performances.As required, can add other packing materials: talcum powder, glass microballon, glass platelet sheet etc.Can also add fire retardant: bromine compounds such as bromo polycarbonate, brominated epoxy resin, phosphoric acid fat etc. contains the compound of phosphoric, antimony compoundss such as antimonous oxide, antimony peroxide etc.Can also add molecule chain end properties-correcting agent, buffering modifying agent, dissolve promotor etc. mutually the resin combination performance is further improved.
In addition, as required, without detriment to the resin combination performance or under, can add the parting agent of suitable type and suitable proportion, oxidation hold back agent, the transesterify hold back agent that prevents transesterification reaction and the tinting material etc. of anti-oxidation to the little prerequisite of the loss of resin combination performance.Also can add carbon black, metal fine powder waits and reduces insulativity, reach conduction or prevent the electrostatic purpose.
Manufacture method for the resin combination among the present invention does not need to be limited especially.All compositions can be mixed, the blend compositions that obtains directly as the raw material of purposes such as moulding.Also can utilize closed mixing machine, extrusion machine etc., blend compositions is carried out the fusion extrusion molding that mixes, the resin combination that extrusion molding is obtained is as the raw material of purposes such as moulding.Concrete hybrid mode during for resin combination also needn't be limited, can with each composition in after fixed ratio weighing mixes, carry out disposable mixed; After also can in advance a part of composition being mixed, other remaining compositions are added to the former carry out property mixing stage by stage.
Resin combination of the present invention is fit to various production and processing methods such as extrusion process, rotation-formed method, slush molding method, compressed moulding method, injection moulding, especially applicable to the process for processing mode of low temperature injection molding, fast injection moulding, the moulding product that utilize this component thing to manufacture out have the high feature of crystallization degree.Resin combination of the present invention can be used in the structural part of manufacturing various electronic products, electric product, instrument, mechanical implement, automobile and other industries, the plastics film of purposes such as packing, the tubular products of the loose sleeve pipe of electricwire conduit, fiber optics etc. and the engineering plastics starting material of other goods.
The present invention has adopted and has added the p-hydroxybenzenyl sulfonate an alkali metal salt increases the nuclear agent as crystallization method, provide a kind of polypropylene terephthalate's thermoplastic resin composition and its products, the slow-paced major defect of crystallization when fundamentally solving propylene glycol ester terephthalate's resinoid as the industrial plastic material.
Excellent results of the present invention is embodied as:
1. provide and have higher crystallization speed and the good thermoplastically polyester family tree oil/fat composition of heat-resistant stability energy.
2. provide have the degree of crystallization height, degree of crystallinity is evenly distributed, and has the thermoplastically polyester family tree oil/fat composition moulding product of favorable mechanical mechanical property.
(4) embodiment
Below in conjunction with embodiment, the present invention is done detailed elaboration, but content of the present invention is not limited to these specific embodiments.
Embodiment 1: thermoplastic resin composite, and component is as follows:
(a) PTT resin, accounting for the composition weight ratio is 99.7%;
(b) p-hydroxy benzenyl sulfonate sodium salt, accounting for the composition weight ratio is 0.3%;
Above-mentioned (a) PTT resin is with terephthalic acid (PTA) and 1, and ammediol is the polymkeric substance that main component obtains by the direct esterification method.Under 30 ℃ temperature condition, when measuring with the mixing solutions of 1: 1 methylene dichloride of weight ratio (methylene chloride) and trifluoracetic acid (trifluoroacetic acid), the intrinsic viscosity of PTT resin is 0.92dl/g.
The material of above-mentioned (b) p-hydroxy benzenyl sulfonate sodium salt by obtaining with chemical reaction in p-hydroxybenzenyl sulfonate and the sodium hydroxide, the hydroxyl of p-hydroxybenzenyl sulfonate and sulfonic group are 95% by sodium ion neutral degree (degree of neutralization).
Comparative example 1: do not add the PTT resin that crystallization increases the nuclear agent.
As the Comparative Examples of embodiment 1, have only the PTT resinous principle, the crystallization that does not add any kind of increases the nuclear agent.
Comparative example 2: the PTT resin combination that increases the nuclear agent with the stearic acid an alkali metal salt as crystallization.
As described in embodiment 1, different is to have substituted (b) p-hydroxy benzenyl sulfonate sodium salt with the stearic acid sodium salt.
Comparative example 3: the PTT resin combination that increases the nuclear agent with the M-nitro benzoic acid an alkali metal salt as crystallization.
As described in embodiment 1, different is to have substituted (b) p-hydroxy benzenyl sulfonate sodium salt with the phenylformic acid sodium salt.
Comparative example 4: the thermoplastic resin composite that increases the nuclear agent with the P-hydroxybenzoic acid an alkali metal salt as crystallization.
As described in embodiment 1, different has been with the P-hydroxybenzoic acid sodium salt to replace (b) p-hydroxy benzenyl sulfonate sodium salt.The material of the p-hydroxy benzenyl sulfonate sodium salt that is adopted by obtaining with chemical reaction in P-hydroxybenzoic acid and the sodium hydroxide, hydroxyl and formyloxy are 93.5% by sodium ion institute neutral degree.
Embodiment 2:
As described in embodiment 1, different is (a) PTT resin, and accounting for the composition weight ratio is 99.4%, (b) p-hydroxy benzenyl sulfonate sodium salt, and accounting for the composition weight ratio is 0.6%.
Embodiment 3:
As described in embodiment 1, different is that (b) component is a p-hydroxybenzenyl sulfonate sylvite.
Embodiment 4:
As described in embodiment 1, different is that (b) component is the p-hydroxybenzenyl sulfonate lithium salts.
Embodiment 5: increase the fiber reinforcement thermoplastic resin composite of examining agent with the p-hydroxybenzenyl sulfonate an alkali metal salt as crystallization, component is as follows:
(a) PTT resin, accounting for the composition weight ratio is 69.7%;
(b) p-hydroxy benzenyl sulfonate sodium salt, accounting for the composition weight ratio is 0.3%;
(c) fortifying fibre composition: glass fibre, Fibre diameter 12 μ m, accounting for composition weight per-cent is 30.0%.
(a) PTT resin that adopts and (b) p-hydroxy benzenyl sulfonate sodium salt as described in the embodiment 1.
Comparative example 5: do not add the fiber reinforcement thermoplastic resin composite that crystallization increases the nuclear agent.
The fiber reinforcement thermoplastic resin composite that is comparative example 5 with 5 differences of embodiment by (a) PTT resinous principle and (c) fortifying fibre form, the crystallization that does not add any kind of increases the nuclear agent.
Comparative example 6: the fiber reinforcement thermoplastic resin composite that increases the nuclear agent with the M-nitro benzoic acid an alkali metal salt as crystallization.
As described in embodiment 5, different is to have substituted (b) p-hydroxy benzenyl sulfonate sodium salt with the phenylformic acid sodium salt.
Comparative example 7: the fiber reinforcement thermoplastic resin composite that increases the nuclear agent with the P-hydroxybenzoic acid an alkali metal salt as crystallization.
As described in embodiment 5, different has been with the P-hydroxybenzoic acid sodium salt to replace (b) p-hydroxy benzenyl sulfonate sodium salt.The p-hydroxy benzenyl sulfonate sodium salt that adopts is as described in the comparative example 4.
Embodiment 6: increase the fiber reinforcement thermoplastic resin composite of examining agent with the p-hydroxybenzenyl sulfonate an alkali metal salt as crystallization, component is as follows:
(a) PTT resin, accounting for the composition weight ratio is 89.7%;
(b) p-hydroxy benzenyl sulfonate sodium salt, accounting for the composition weight ratio is 0.3%;
(c) fortifying fibre composition: carbon fiber, accounting for composition weight per-cent is 10.0%.(a) PTT resin that adopts and (b) p-hydroxy benzenyl sulfonate sodium salt as described in the embodiment 1.
Embodiment 7:
As described in embodiment 5, different is that (a) component is to mix the PTT resinoid of PET resin.Wherein the PTT resin accounts for 71.7% weight percent of (a) component, and the PET resin accounts for 28.3% weight percent of (a) component.
Embodiment 8:(b) component increases the fiber reinforcement thermoplastic resin composite of examining agent for the composite junction crystallization, and component is as follows:
(a) PTT resin, accounting for composition weight per-cent is 69.2%,
(b) component is that the composite junction crystallization increases the nuclear agent, accounting for composition weight per-cent is 0.8%, wherein the sodium ion of p-hydroxy benzenyl sulfonate sodium salt accounts for 48.0% mol ratio of sodium ion total amount in this component, the sodium ion of ethylene-methacrylic acid copolymer sodium ion cross-linked polymer accounts for 52.0% mol ratio of sodium ion total amount in this component
(c) fortifying fibre composition: glass fibre, accounting for composition weight per-cent is 30.0%.
Embodiment 9:
As described in embodiment 5, institute's difference is that (b) component is that the composite junction crystallization increases the nuclear agent, wherein the sodium ion of p-hydroxy benzenyl sulfonate sodium salt accounts for 74.3% mol ratio of sodium ion total amount in this component, and the sodium ion of P-hydroxybenzoic acid sodium salt accounts for 25.7% mol ratio of sodium ion total amount in this component.
Embodiment 10:
As described in embodiment 8, different is with average diameter of particles is that the talcum micro mist of 0.5 μ m has replaced ethylene-methacrylic acid copolymer sodium ion cross-linked polymer.Wherein the sodium ion of p-hydroxy benzenyl sulfonate sodium salt accounts for 100% mol ratio of sodium ion total amount in this component.
Be exemplary with embodiment 1, embodiment 2 and embodiment 5 and their comparative example below, embodiment be described in more details:
By behind each composition of prescription weighing of above-mentioned record, carry out uniform mixing, mixture is added in the extruding machine from opening for feed, the extrusion molding that mixes under molten state with the plastic ties of city's water cooling molten state, carries out pelletizing then.This extrusion process is φ 30mm, rotates on two extruding machine molding machines and finish in the same way at a screw diameter.During extrusion molding, the bushing temperature of extruding machine is set at 250 ℃
One, the mechanical mechanics property test evaluation is set forth with the preparation and the various evaluation method of sample.
Estimate preparation: after the above-mentioned plastic grain that obtains being carried out 120 ℃, 8 hours vacuum-drying, utilize injection moulding machine processing machinery mechanical property evaluation ASTM sample with sample.Processing conditions during injection molding is as follows: 250 ℃ of the bushing temperatures of injection moulding machine, and inject time and dwell time add up to 10 seconds, and the mould internal cooling time is 10 seconds.When preparing the sample of the resin combination that does not contain the fortifying fibre composition, the temperature of forming mould is set at 80 ℃; When preparing the sample of fiber-reinforced resin composition, the temperature of forming mould is set at 20 ℃ and 80 ℃ respectively.
Various evaluation methods:
(1) measurement of melt viscosity
270 ℃ of temperature, cut off speed γ=912sec
-1Condition under, according to common mensuration program, utilize capillary rheometer that plastic grain is carried out melt viscosity and measure.
(2) evaluation of crystallization speed
Dsc measurement: from the plastic grain that obtains by extrusion molding, cut out the broken end about 5～7mg, after inserting special little aluminium dish and sealing, on differential thermal scanner (DSC, the PYRISDiamond DSC that has utilized PERKIN ELMER company to produce in this measurement), measure.Heat-up rate with 20 ℃/min is warming up to 280 ℃ from room temperature, and in 280 ℃ of maintenances 3 minutes, the heat release of carrying out in the temperature-fall period with the cooling rate of 20 ℃/min was measured then.The peak temperature of resulting exotherm is crystallized temperature Tc, and the temperature amplitude of exotherm peak half value is Δ Tc.As the index of weighing crystallization speed, the Tc value is high more, and Δ Tc value is more little, shows that crystallization speed is fast more.
By relatively obtaining Tc value and Δ Tc value, can estimate the crystallization speed difference between different PTT resin combinations by dsc measurement.
(3) mechanics of machinery evaluating characteristics
Carried out the measurement that stretching is estimated and bending is estimated based on ASTM-D638 and ASTM-D790 criterion; Based on the ASTM-D256 criterion, utilizing thickness is 1/8 inch, sample jaggy, has carried out the measurement of shock-resistant evaluation.
Two, about the evaluation result of melt viscosity, crystallization speed and mechanical mechanics property
(1) about the evaluation result of the various resin combinations that do not contain the fortifying fibre composition:
Table 1 is about the crystallization velocity of the plastic grain of the various resin combinations that do not contain the fortifying fibre composition that obtained by melt extrusion and the measuring result of melt viscosity.
Table 1 does not contain the melt viscosity of various resin combinations of fortifying fibre composition and the measuring result of crystallization speed
| Crystallization increases the kind of nuclear agent | The sodium ion amount (scaled value, ppm) | Melt viscosity (PaSec) | Crystallized temperature Tc (℃) | ΔTc (℃) | The ascensional range of Tc (℃) | |
| Embodiment 1 | P-hydroxy benzenyl sulfonate sodium salt | 217 | 109.4 | 182.7 | 5.4 | 5.5 |
| Embodiment 2 | P-hydroxy benzenyl sulfonate sodium salt | 434 | 109.2 | 189.5 | 4.3 | 12.2 |
| Comparative example 1 | --- | 0 | 110.0 | 177.3 | 7.5 | - |
| Comparative example 2 | The stearic acid sodium salt | 225 | 65.7 | 179.4 | 5.4 | 2.1 |
| Comparative example 3 | The phenylformic acid sodium salt | 479 | 62.4 | 184.1 | 6.6 | 6.8 |
| Comparative example 4 | The P-hydroxybenzoic acid sodium salt | 377 | 69.4 | 187.1 | 4.3 | 9.9 |
Compare with comparative example 1 (crystallization that does not add any kind of increases the composition of examining agent), the crystallized temperature Tc of embodiment 1 (having added weight percent and be the resin combination of 0.3% p-hydroxy benzenyl sulfonate sodium salt), embodiment 2 (having added weight percent and be the resin combination of 0.6% p-hydroxy benzenyl sulfonate sodium salt) exceeds 5.5 ℃, 12.2 ℃ respectively, the temperature amplitude Δ Tc of exotherm peak half value narrows down to 5.4 ℃ and 4.3 ℃ respectively from 7.5 ℃, and melt viscosity remains unchanged substantially.Illustrate that the crystallization speed of PTT resin combination is improved to a great extent, and does not cause PTT resin generation pyrolysated phenomenon owing to added a spot of p-hydroxy benzenyl sulfonate sodium salt.
Comparative example 2, comparative example 3 and comparative example 4 are respectively to have added to account for the PTT resin combination that composition weight per-cent is 0.3% stearic acid sodium salt, phenylformic acid sodium salt and P-hydroxybenzoic acid sodium salt.Because the alkali metallic sodium ionic exists, the crystallized temperature Tc of comparative example 2, comparative example 3 and comparative example 4 and the exotherm peak half value temperature amplitude Δ Tc improvement that also is improved to a great extent, but their melt viscosity value does not increase low many of the melt viscosity value of resin combination of nuclear agent than adding crystallization, illustrate because a spot of stearic acid sodium salt, phenylformic acid sodium salt and the P-hydroxybenzoic acid sodium salt that adds causes the PTT resin that more serious thermolysis has taken place.
In addition, with regard to the sodium ion conversion amount of adding, embodiment 1 and comparative example 2, embodiment 2 is in identical rank respectively with the sodium ion amount that comparative example 3, comparative example 4 are contained, data according to table 1, we can learn that p-hydroxy benzenyl sulfonate sodium salt is higher than the efficient of other organic sodium salt for the crystallization speed that promotes the PTT resin.On chemical structure, though p-hydroxy benzenyl sulfonate sodium and P-hydroxybenzoic acid sodium have only the difference of sulfonic group and formyloxy, in fact p-hydroxy benzenyl sulfonate sodium increases the better effects if of nuclear agent as crystallization.
Table 2 is the evaluation results about the mechanical mechanics property of the ASTM sample of the various resin combinations that do not contain the fortifying fibre composition.
Table 2 does not contain the mechanical mechanics property of ASTM sample of the various resin combinations of fortifying fibre composition
| Tensile strength (MPa) | Extension at break degree (%) | Flexural strength (MPa) | Modulus in flexure (GPa) | Impact strength (J/m) | |
| Embodiment 1 | 61.4 | 5.8 | 102 | 2.87 | 32 |
| Embodiment 2 | 62.0 | 5.4 | 103 | 2.94 | 32 |
| Comparative example 1 | 60.5 | 12.9 | 101.2 | 2.67 | 32 |
| Comparative example 2 | 50.1 | 2.9 | 105.0 | 3.21 | 25 |
| Comparative example 3 | 55.0 | 3.2 | 105.0 | 2.99 | 27 |
| Comparative example 4 | 59.2 | 2.6 | 102.6 | 2.97 | 25 |
As can be seen from Table 2 and comparative example 1 compare, embodiment 1 and implement 2 mechanical mechanics property and remove extension at break and be outside one's consideration is not damaged, most of indexs even have are slightly improved.Based on the melt viscosity data of table 1, the reason that our deducibility extension at break degree descends is not because the reduction of PTT molecular resin amount, but because the increase of the degree of crystallinity of moulding product causes that this result is reasonable, easy understanding.Yet, the mechanical mechanics property of comparative example 2, comparative example 3 and comparative example 4, because the reduction significantly of a spot of stearic acid sodium salt, phenylformic acid sodium salt and the caused PTT molecular resin of the P-hydroxybenzoic acid sodium salt amount of adding, find expression in the decline significantly of melt viscosity value particularly, thus in tensile strength, split extensibility and the impact strength everyway presents tangible deterioration.
(2) about the evaluation result of the various resin combinations that contain the fortifying fibre composition:
Table 1 is about the crystallization velocity of the plastic grain of the various resin combinations that contain the fortifying fibre composition that obtained by melt extrusion and the evaluation result of melt viscosity.
Table 3 contains the melt viscosity of various resin combinations of fortifying fibre composition and the measuring result of crystallization speed
| Crystallization increases the kind of nuclear agent | Melt viscosity (PaSec) | Crystallized temperature Tc (℃) | ΔTc (℃) | The rising spoke degree of Tc (℃) | |
| Embodiment 5 | P-hydroxy benzenyl sulfonate sodium salt | 192.8 | 188.1 | 3.8 | 11.1 |
| Comparative example 5 | --- | 193.0 | 177.0 | 9.3 | -- |
| Comparative example 6 | The phenylformic acid sodium salt | 129.5 | 183.8 | 6.8 | 6.8 |
| Comparative example 7 | The P-hydroxybenzoic acid sodium salt | 136.5 | 189.4 | 3.5 | 12.4 |
Compare with comparative example 5 (crystallization that does not add any kind of increases the glass fiber-reinforced resin composition of examining agent), the crystallized temperature Tc of the crystallized temperature Tc comparative example 5 of embodiment 5 (added and accounted for the glass fiber-reinforced resin composition that composition weight per-cent is 0.3% p-hydroxy benzenyl sulfonate sodium salt) exceeds 11.1 ℃, Δ Tc has narrowed down to 3.8 ℃ from 9.3 ℃, and melt viscosity does not have to change substantially.Illustrate that the crystallization speed that glass fibre strengthens the PTT resin combination is improved to a great extent owing to added a spot of p-hydroxy benzenyl sulfonate sodium salt, and thermolysis does not take place in PTT resin basically.
Comparative example 6 and comparative example 7 are respectively to have added that to account for composition weight per-cent be that the glass fibre of 0.3% phenylformic acid sodium salt and P-hydroxybenzoic acid sodium salt strengthens the PTT resin combination.This result situation with the above-mentioned resin combination that does not contain the fortifying fibre composition basically is identical, because the alkali metallic sodium ionic exists, the improvement that also is improved to a great extent of the Tc value of comparative example 6 and comparative example 7 and Δ Tc value, but the crystallization that does not add any kind of increases the comparative example 5 of nuclear agent compares, their melt viscosity value is greatly reduced, illustrate because a spot of stearic acid sodium salt, phenylformic acid sodium salt and the P-hydroxybenzoic acid sodium salt that adds, caused that the PTT resin thermolysis has taken place, caused the decline of molecular weight.
Table 4 is the mechanical mechanics property evaluation results about the ASTM sample of the various resin combinations that contain the fortifying fibre composition.
Table 4 contains the mechanical mechanics property of ASTM sample of the various resin combinations of fortifying fibre composition
| Forming temperature | Tensile strength (MPa) | Extension at break degree (%) | Flexural strength (MPa) | Modulus in flexure (GPa) | Impact strength (J/m) | |
| Embodiment 5 | 20℃ | 141.3 | 4.0 | 214.0 | 9.34 | 73 |
| 80℃ | 142.0 | 3.8 | 211.3 | 9.48 | 75 | |
| Comparative example 5 | 20℃ | 116.0 | 3.6 | 211.3 | 8.84 | 133 |
| 80℃ | 139.8 | 4.2 | 218.1 | 9.23 | 76 | |
| Comparative example 6 | 20℃ | 125.9 | 3.2 | 175.0 | 9.55 | 72 |
| 80℃ | 120.1 | 3.0 | 168.0 | 9.58 | 71 | |
| Comparative example 7 | 20℃ | 130.8 | 3.5 | 182.3 | 9.50 | 78 |
| 80℃ | 129.0 | 3.4 | 172.9 | 9.51 | 77 |
As can be seen from Table 4, the low temperature moulding product of comparative example 5 (during moulding, die temperature is 20 ℃), between typical temperature moulding product (during moulding, die temperature is 80 ℃), tensile strength exists evident difference.The low temperature moulding product are owing to the degree of crystallization deficiency, and tensile strength is bad, modulus in flexure is on the low side.Though the impact strength of low temperature moulding product is very good, tracing it to its cause also is owing to the insufficient of degree of crystallization causes.
Added between the low temperature moulding product and typical temperature moulding product of glass fiber-reinforced resin composition (embodiment 5) of p-hydroxy benzenyl sulfonate sodium salt, there is not very big difference in mechanical mechanics property, and all mechanical mechanics property indexs all mechanical mechanics property data with the typical temperature moulding product of comparative example 5 are close.The crystallization speed that the resin Composition thing of embodiment 5 is described has reached quickish degree, can be adapted to the process for processing of low temperature moulding.
Mechanical mechanics property about comparative example 6 and comparative example 7, because a spot of phenylformic acid sodium salt that adds and the thermolysis of the caused PTT resin of P-hydroxybenzoic acid sodium salt, the reduction of molecular weight, no matter be low temperature moulding product or typical temperature moulding product, do not add the common moulding product of fiber-reinforced resin composition that crystallization increases the nuclear agent and compare, all presenting tangible deterioration aspect tensile strength and the flexural strength.
In sum, the p-hydroxybenzenyl sulfonate an alkali metal salt is that the crystallization of the very outstanding promotion PTT resinoid crystallization speed of a class increases the nuclear agent.Thermoplastically polyester family tree oil/fat composition of the present invention has higher crystallization speed and good heat-resistant stability, applicable to the process for processing mode of low temperature moulding, fast injection moulding.Have with the prepared product of PTT based resin composition of the present invention that degree of crystallization is higher, degree of crystallinity is evenly distributed and the characteristics of favorable mechanical mechanical property.
Claims (8)
1. thermoplastic resin composite is characterized in that, comprises following component, all is weight percentage:
(a) polypropylene terephthalate's resin perhaps mixes polypropylene terephthalate's resin of other resins, surplus,
Above-mentioned polypropylene terephthalate's resin is 1: 1 methyl chloride and a trifluoroacetic mixing solutions with weight ratio, and when measuring under the condition of 30 ℃ of temperature, intrinsic viscosity is 0.4dl/g～1.6dl/g scope;
Above-mentioned polypropylene terephthalate's resin is with terephthalic acid and 1, the polymkeric substance that the polycondensation that ammediol is a main component by direct condensation obtains, perhaps with dimethyl terephthalate (DMT) and 1, the polymkeric substance that the polycondensation that ammediol is a main component by transesterify obtains; Other resinous principles that mix account for below 50% of (a) component;
(b) p-hydroxybenzenyl sulfonate an alkali metal salt crystallization increases the nuclear agent, and the composite junction crystallization that perhaps contains the p-hydroxybenzenyl sulfonate an alkali metal salt increases the nuclear agent, and 0.005%～6%,
(c) fortifying fibre, 0～65%.
2. thermoplastic resin composite as claimed in claim 1, it is characterized in that, the basic metal of p-hydroxybenzenyl sulfonate an alkali metal salt is meant lithium, sodium, potassium in described (b) component, wherein the hydroxyl of p-hydroxybenzenyl sulfonate and sulfonic group are accounted for hydroxyl and sulfonic group total amount 30% mol ratio～100% mol ratio by alkalimetal ion neutral degree.
3. thermoplastic resin composite as claimed in claim 1, it is characterized in that, in described (b) component the composite junction crystallization increase nuclear agent be meant, increase in the nuclear agent p-hydroxybenzenyl sulfonate an alkali metal salt at crystallization, one or more that select to add talcum powder inorganic micro powder, P-hydroxybenzoic acid an alkali metal salt, ethylene-methacrylic acid copolymer alkali metal ionomers salt increase the nuclear agent as second crystallization, and the alkalimetal ion amount of p-hydroxybenzenyl sulfonate an alkali metal salt accounts for more than 30% mol ratio that the composite junction crystallization increases alkalimetal ion total amount in the nuclear agent.
4. thermoplastic resin composite as claimed in claim 1 is characterized in that, used fiber is the glass fibre of diameter at 3 μ m～30 mu m ranges in described (c) component.
5. be the product that raw material is made with the described thermoplastic resin composite of claim 1.
6. thermoplastic resin composite as claimed in claim 5 is the product that raw material is made, it is characterized in that, and be the structural member of electrical and electronic product, instrument, automobile, mechanical implement.
7. thermoplastic resin composite as claimed in claim 5 is the product that raw material is made, it is characterized in that, and be plastic membrane product.
8. thermoplastic resin composite as claimed in claim 5 is the product that raw material is made, it is characterized in that, and be the plastic tube-shape goods.
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Assignee: Changxing (Guangzhou) Fine Paint Co., Ltd. Assignor: Shandong University Contract fulfillment period: 2007.1.4 to 2012.1.3 contract change Contract record no.: 2009440001052 Denomination of invention: Thermoplastic resin composition and product thereof Granted publication date: 20050518 License type: Exclusive license Record date: 2009.8.5 |
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