CN103102475B - A kind of talcum powder-polyester composite and preparation method thereof - Google Patents
A kind of talcum powder-polyester composite and preparation method thereof Download PDFInfo
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- CN103102475B CN103102475B CN201110356560.7A CN201110356560A CN103102475B CN 103102475 B CN103102475 B CN 103102475B CN 201110356560 A CN201110356560 A CN 201110356560A CN 103102475 B CN103102475 B CN 103102475B
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Abstract
The present invention relates to a kind of talcum powder-polyester composite and preparation method thereof, the method comprises the following steps: (1) mixes the water of the ethylene glycol of the coupling agent of 1 weight portion, 10-100 weight portion and 0.1～10 weight portion, with acid for adjusting pH value be 1～6, be hydrolyzed 0～1 hour; (2) coupling agent hydrolyzate is mixed with the talcum powder of 30～1000 weight portions, incorporation time is 5min, obtains active talcum powder; (3) ethylene glycol of the terephthalic acid (TPA) of active talcum powder 0.1-10 weight portion and 70-80 weight portion, 20-30 weight portion is uniformly mixed, add catalyst 0.01-1 weight portion, be warming up to 70～90 DEG C, vacuum dehydration is to water content < 1.0%, be warming up to again 220～240 DEG C of esterification 6-10 hour, add additive 0.01-1 weight portion, and to be evacuated to vacuum at 240 DEG C～260 DEG C be below 80Pa, polymerisation 1-3 hour, obtains product.
Description
Technical field
The present invention relates to polymer composite field, especially relate to a kind of talcum powder-polyester composite andIts preparation method.
Background technology
PETG (PET) is topmost kind in thermoplastic polyester, resistance to creep and fatiguePerformance is good, and case hardness is high, and mechanical performance and thermosetting plastics are close, is widely used in fiber, film.But PET heat distortion temperature is low, and crystalline rate is low, poor dimensional stability, has limited it in engineering plasticsExtensive use.
Talcum powder main component is hydrated magnesium silicate, has more stable lamellar structure, is that a kind of China dividesCloth is inorganic mineral material widely. Talcum powder is widely used in the filling-modified of plastics, has raising plastics machineTool performance, heat resistance, barrier, dimensional stability, reduce the warpage properties of plastics, the effect reducing costs.Discovered in recent years superfine talcum powder has the effect that promotes nucleation as the crystallization nucleating agent of PET.
Cui Zheng etc. " PET/ talcum powder compound material crystal property, hot property and mechanical property research " (" inState's plastics " the 23rd volume o. 11th) in find in PET, add after 0.5% superfine talcum powder, thermal deformationTemperature, hot strength, bending strength are improved; Yang Qingquan etc. are at " PA66/PET/ talcum powder composite woodMaterial research " in (" Chinese Plastics " the 22nd the 7th phase of volume), find to add after 5%～10% talcum powder, compoundHeat distortion temperature and the mechanical property of material are improved.
Talcum powder is to carry out blend granulation again with existing PET raw material as nucleator at present, need to carry outRear processing, the present invention with coupling agent treatment, is coated talcum powder surface at raw material synthesis phase and PET original positionCopolymerization, makes the composite that crystal property is good.
Summary of the invention
The invention provides talcum powder-polyester that a kind of compatibility is high, coupling agent consumption is little, original position is coated copolymerization multipleCondensation material and preparation method thereof.
Object of the present invention can be achieved through the following technical solutions:
A kind of talcum powder-polyester composite, is characterized in that, this material is by the component that comprises following weight portionMake:
Active talcum powder 0.1-10;
Terephthalic acid (TPA) (PTA) 70-80;
Ethylene glycol (EG) 20-30;
Catalyst 0.01-1;
Additive 0.01-1.
Described active talcum powder is to be prepared from by the following method: by the coupling agent of 1 weight portion, 10-100The ethylene glycol of weight portion and the water of 0.1～10 weight portion mix, with acid for adjusting pH value be 1～6, enterRow hydrolysis 0～1 hour, obtains coupling agent hydrolyzate, by this coupling agent hydrolyzate and 30～1000 weight portionsTalcum powder mixes, and incorporation time is 5～10min, obtains the active talcum powder through coupling agent activation.
Described talcum powder particle diameter order number is not less than 1200 orders, preferably 6000-10000 order; Described couplingAgent is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane or VTES; Described useAcid for adjusting pH value acid used comprises one or more in oxalic acid, hydrochloric acid or sulfuric acid.
Described catalyst is antimony acetate or antimony oxide.
Described additive is diisopropylamine.
Described terephthalic acid (TPA) is the refining terephthalic acid (TPA) of monomer.
A preparation method for talcum powder-polyester composite, is characterized in that, the method comprises the following steps:By the second of the terephthalic acid (TPA) of active talcum powder 0.1-10 weight portion and 70-80 weight portion, 20-30 weight portionGlycol is uniformly mixed, and forms stable suspended substance, adds catalyst 0.01-1 weight portion, is warming up to 70-90DEG C, vacuum dehydration is to water content < 1.0%, then is warming up to 220～240 DEG C of esterification 6-10 hour, adds interpolationAgent 0.01-1 weight portion, and to be evacuated to vacuum at 240-260 DEG C be below 80Pa, polymerisation 1-3Hour, obtain product.
Compared with prior art, the preparation of product of the present invention comprises talcous coupling agent coating activation, activityTalcum powder and organic monomer carry out glycerol polymerization, make talcum powder-polyester composite through a series of processing, slidingThe affinity of talcum powder and PET resin can be effectively improved on stone flour surface by coupling agent coating. The talcum makingPowder-polyester composite, forms between talcum powder and PETG through coupling agent covalent bond phaseThe special construction connecting, the formation of this structure can effectively improve the table of talcum powder and PETGFace affinity. Talcum powder plays heterogeneous nucleating effect in PET simultaneously, improves the crystal property of PET,Thereby hot property, the strength and stiffness of PET are improved.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Get the solution of 0.2g coupling agent VTES, 5g ethylene glycol, the configuration of 1g water, with grassAcid for adjusting pH value is 6, is hydrolyzed 1 hour, crosses the talcum powder blend 5min of 1250 mesh sieves with 200g,Through the talcum powder of coupling agent activation, for subsequent use. Get activated talc powder 41.9g, add PTA290g, EG129g,Catalyst acetic acid antimony 0.13g, mix and blend. After drawing water and being less than 1% to water content, begin to warm to 70 DEG C and enterRow esterification. Under normal pressure, after 8 hours, add additive diisopropylamine 220～240 DEG C of esterifications0.01g, being evacuated to vacuum is below 80Pa, 240 DEG C of polymerisations 3 hours, obtains requiredThe PET/ talcum powder compound material of wanting. Gained composite property is in table 1.
Embodiment 2
Get 0.2g coupling agent N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 5g ethylene glycol, 1g waterConfiguration solution, with careless acid for adjusting pH value be 6, be hydrolyzed 1 hour, with the talcum of 200g10000 order particle diameterPowder blend 5min, obtains the talcum powder through coupling agent activation, for subsequent use. Get activated talc powder 16g, addPTA290g, EG129g, catalyst acetic acid antimony 0.13g, mix and blend. After drawing water and being less than 1% to water content,Begin to warm to 90 DEG C and carry out esterification. Under normal pressure, after 8 hours, add interpolation 220～240 DEG C of esterificationsAgent diisopropylamine 0.01g, being evacuated to vacuum is below 80Pa, 250 DEG C of polymerisations 3 hours,Obtain needed PET/ talcum powder compound material. Gained composite property is in table 1.
Comparative example
Compare with the existing polyester material in market, trade mark PETCZ328, Jiangyin, the place of production is industrial.
The sample preparation in injection machine with PETCZ328 material or self-control talcum powder-PET composite, temperature settingBe set to 260 DEG C, 260 DEG C, 255 DEG C, 255 DEG C, batten test result is as follows:
The each properties of product test result of table 1: embodiment:
Drawn by table 1 data: the prepared talcum powder-polyester composite of the present invention ensure hot strength,When bending strength and impact strength, have better than existing pet materialHeat resistance and structural stability, and save cost, technique is simple.
Embodiment 3
Get 1g coupling agent N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 10g ethylene glycol, 0.1g waterConfiguration solution, with salt acid for adjusting pH value be 6, be hydrolyzed 1 hour, with the talcum powder of 30g3000 order particle diameterBlend 5min, obtains the activated talc powder through coupling agent activation, for subsequent use. Get activated talc powder 0.27g, addEnter PTA210g, EG60g, catalyst acetic acid antimony 0.01g, mix and blend. Draw water to water content and be less than 1%After, begin to warm to 80 DEG C and carry out esterification. Under normal pressure,, after 6 hours, add and add 220 DEG C of esterificationsPpd b isopropylamine 0.01g, being evacuated to vacuum is below 80Pa, little 260 DEG C of polymerisations 3Time, obtain needed PET/ talcum powder compound material.
Embodiment 4
Get the solution of 1g coupling agent VTES, 100g ethylene glycol, the configuration of 1g water, with grassAcid for adjusting pH value is 1, is hydrolyzed 1 hour, crosses the talcum powder blend 5min of 6000 order particle diameters with 1000g,The activated talc powder that must activate through coupling agent, for subsequent use. Get activated talc powder 20g, add PTA240g, EG90g,Catalyst acetic acid antimony 1g, mix and blend. After drawing water and being less than 1% to water content, start to heat up 80 DEG C and carry out esterChange reaction. Under normal pressure, after 10 hours, add additive diisopropylamine 1g 230 DEG C of esterifications, take out trueEmpty to vacuum be below 80Pa, 250 DEG C of polymerisations 3 hours, obtain needed PET/ slidingStone flour composite.
Embodiment 5
Get the solution of 0.2g coupling agent VTES, 5g ethylene glycol, the configuration of 1g water, use sulphurAcid for adjusting pH value is 6, is hydrolyzed 1 hour, crosses the talcum powder blend 5min of 1250 mesh sieves with 200g,Through the talcum powder of coupling agent activation, for subsequent use. Get activated talc powder 41.9g, add PTA290g, EG129g,The catalytic antimony trioxide 0.13g, mix and blend. After drawing water and being less than 1% to water content, start to heat up and carry outEsterification. Under normal pressure, after 8 hours, add additive diisopropylamine 0.01g 220～240 DEG C of esterifications,Being evacuated to vacuum is below 80Pa, 240 DEG C of polymerisations 3 hours, obtains needed PET/Talcum powder compound material.
Claims (6)
1. talcum powder-polyester composite, is characterized in that, this material is by comprising following weight portionComponent is made:
Described active talcum powder is to be prepared from by the following method: by the coupling agent of 1 weight portion, 10-100The ethylene glycol of weight portion and the water of 0.1～10 weight portion mix, with acid for adjusting pH value be 1～6, enterRow hydrolysis 0～1 hour, obtains coupling agent hydrolyzate, by this coupling agent hydrolyzate and 30～1000 weight portionsTalcum powder mixes, and incorporation time is 5～10min, obtains the active talcum powder through coupling agent activation;
Described additive is diisopropylamine.
2. a kind of talcum powder-polyester composite according to claim 1, is characterized in that, described inTalcum powder particle diameter order number be not less than 1200 orders; Described coupling agent is N-(β-aminoethyl)-γ-aminopropyl threeMethoxy silane or VTES; Described with acid for adjusting pH value acid used comprise oxalic acid,One or more in hydrochloric acid or sulfuric acid.
3. a kind of talcum powder-polyester composite according to claim 2, is characterized in that, described inTalcum powder particle diameter order number be 6000-10000 order.
4. a kind of talcum powder-polyester composite according to claim 1, is characterized in that, described inCatalyst be antimony acetate or antimony oxide.
5. a kind of talcum powder-polyester composite according to claim 1, is characterized in that, described inTerephthalic acid (TPA) be the refining terephthalic acid (TPA) of monomer.
6. a preparation method for talcum powder-polyester composite as claimed in claim 1, its feature existsIn, the method comprises the following steps: by active talcum powder 0.1-10 weight portion and 70-80 weight portion to benzeneThe ethylene glycol of dioctyl phthalate, 20-30 weight portion is uniformly mixed, and forms stable suspended substance, adds catalysisAgent 0.01-1 weight portion, is warming up to 70-90 DEG C, and vacuum dehydration is to water content < 1.0%, then is warming up to 220～240DEG C esterification 6-10 hour, adds additive 0.01-1 weight portion, and is evacuated to vacuum at 240-260 DEG CBelow 80Pa, polymerisation 1-3 hour, obtains product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333331A (en) * | 2008-08-07 | 2008-12-31 | 上海大学 | High thermotolerance polylactic acid composite material filled by french chalk and method for preparing same |
| CN101709121A (en) * | 2009-11-13 | 2010-05-19 | 厦门德丰行塑胶工业有限公司 | Composite nucleating agent of polyethylene glycol terephthalate and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333331A (en) * | 2008-08-07 | 2008-12-31 | 上海大学 | High thermotolerance polylactic acid composite material filled by french chalk and method for preparing same |
| CN101709121A (en) * | 2009-11-13 | 2010-05-19 | 厦门德丰行塑胶工业有限公司 | Composite nucleating agent of polyethylene glycol terephthalate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 原位聚合复合无机物/PET专用料及其加工改性研究;柯扬船;《中国塑料》;20030930;第17卷(第9期);第44页右栏第1.3节 * |
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