CN102432985A - Method for preparing PET-organic intercalated montmorillonite composite material - Google Patents
Method for preparing PET-organic intercalated montmorillonite composite material Download PDFInfo
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- CN102432985A CN102432985A CN2011103070661A CN201110307066A CN102432985A CN 102432985 A CN102432985 A CN 102432985A CN 2011103070661 A CN2011103070661 A CN 2011103070661A CN 201110307066 A CN201110307066 A CN 201110307066A CN 102432985 A CN102432985 A CN 102432985A
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Abstract
The invention discloses a method for preparing a PET (Polyethylene Terephthalate)-organic intercalated montmorillonite composite material, comprising the following steps of: 1) mixing organic intercalated montmorillonite and fully dried PET according to the weight ratio of 20: 80 to 80: 20 to obtain mixed materials, and preparing the mixed materials into a PET master batch containing the organic intercalated montmorillonite, in which the organic intercalated montmorillonite is obtained by reacting a quaternary phosphonium salt or a silane coupling agent and a sodium montmorillonite intercalation; and 2) uniformly mixing the PET master batch containing the organic intercalated montmorillonite prepared in the step 1) and the PET, so that the mass percentage of the montmorillonite in the mixture is 1-10%; and moulding in an injection way by an injection moulding machine to obtain the product. By mixing the quaternary phosphonium salt or the silane coupling agent organic intercalation modified sodium montmorillonite and the PET to obtain the PET master batch containing the organic intercalated montmorillonite, and then mixing with the pure PET proportionally and moulding in the injection way to obtain the product, the method disclosed by the invention provides a new technology applied to the large-scale production, and can obtain the PET product with good water and gas barrier properties.
Description
Technical field
The present invention relates to organic intercalation montmorillonite composite material technical field, particularly relate to a kind of preparation method of PET-organic intercalation montmorillonite composite material.
Background technology
The material current demand high, that the transparency is good of high barrier, heat resisting temperature is very big.In view of polyethylene terephthalate (being called for short PET) excellent comprehensive performance; Therefore with PET the basis; Method through physics or chemistry is carried out modification; With convenient feasible technological line, making PET is that basic goods have water proof, the choke function that meets the demands, and this becomes one of focus of matrix material research and application.Although PET is better than common plastics aspect ventilative, water-permeable; But vacuum tightness can only be kept 9～12 months; Moisture kept about 3-6 month; Satisfied not the needs that vacuum test tube vacuum tightness, moisture content keep 1.5～2 years validity period, also satisfied not the requirement of carafe, had a strong impact on promoting the use of of product the gas hyposmosis.To the problem of PET barrier property difference, the someone is employed in the way of cover PP pipe in the PET pipe, and the moisture hold-time of pipe is prolonged greatly, satisfy clinical requirement, but this means has influenced transparency of products inevitably, and has increased product cost greatly.
In the prior art, to the study on the modification of PET mainly in the following aspects:
1) with the PEN blend, improves it and refuse water, gas barrier properties.In engineering plastics, PEN is at present best water, the gas-barrier material refused, and its performance index generally are 4～5 times (infiltration rate of carbon dioxide of PET are 15cm3/100inch2.24h.) of PET, have been used to produce Beer Bottle.But it costs an arm and a leg, and is about 4 times of PET, that is to say by 30% reinforced and PET blend; Matrix material blocks water, gas barrier properties improves about 40%; Its moisture, vacuum tightness hold-time approximately prolong about 2～3 months, but this means increase the material cost, make product lack competitiveness.
2) with blend such as spun glass, PS, PE, PP: mainly be the adhesive property that improves PET and blend storeroom, wherein spun glass has very big benefit to the raising of intensity, but whether the raising of gas barrier properties remains further to be confirmed.
3) top coat: mainly contain polyphenylene oxides ester and modifier thereof series, under 0.01～0.06mm coating situation, can improve gas barrier properties more than 3 times, can prolong about 15～18 months of moisture, vacuum tightness hold-time, basic satisfied transportation, storage request for utilization.But this means processing requirement is high, is difficult to scale operation.
By above prior art, no matter be to adopt bilayer sleeve, still coating modified, and adopt the better PEN material of barrier property, all be difficult to accept from the cost angle.
Through being expected to improve the barrier property of PET as container containing with montmorillonite layered salt is compound.Polymer/laminated silicate (polynite is called for short MMT) nano composite material has more advantage, has expanded the range of application of existing macromolecular material, is with a wide range of applications and prospect.Except being widely used in aspects such as film, packing, fiber, these matrix materials can be used for the higher engineering plastics of material performance requirement, container material (as: Beer Bottle, heparin tube etc.).Nearly all in the world major company that relates to polymkeric substance all sets foot in this composite study and development at present.
In the prior art, the method for preparing the PET/MMT nano composite material probably is divided into two big types, that is: in-situ inserted composite algorithm and polymer melt graft process.The PET/ silicate nanometer composite material that uses at present mostly is produced with the technology of in-situ polymerization, and what obtain is exfoliated polymer silicon hydrochlorate stratified composite (PLSN).Wherein, the operational path of in-situ polymerization mainly contains two kinds.The one, MMT is dispersed in the terepthaloyl moietie monomer, polymerization obtains matrix material then.Because MMT forms unsettled colloidal dispersion in terepthaloyl moietie; Thereby to handle MMT; Improve affinity between the two, people such as Beall will use after MMT polar polymer Vinylpyrrolidone polymer (PVP), Z 150PH (PVA) surface treatment of etc.ing and obtain stable colloid in the adding terepthaloyl moietie.Simultaneously suitable polymeric reaction condition will be arranged, make reaction carry out smoothly, MMT has good dispersion state therein.The 2nd, the organism modified MMT is added at polymerization stage; Polymerization obtains matrix material after accomplishing; For example, people such as Frisk add the bottle that MMT makes the PET/MMT nano composite material in the transesterify stage, and the rate of permeation of the packing bottle of test shows matrix material is far below pure PET bottle.Concerning the resin of this industrial scaleization of PET, the operational path that situ aggregation method prepares MMT/PET is complicated, and economic benefit is not high, and the technology of the direct graft process of exploitation melt has urgent demand at present.Wherein, melting intercalation method is applicable on existing contour machining equipment and carries out, and economic benefit is improved greatly, but because MMT disperses more inhomogeneously in polymer melt, causes the intercalation of MMT lamella and peel off and be difficult to realize fully.Barber etc. add PET and leave aggressiveness to increase the reactive force between PET and polynite in compound system, melt extrude then, obtain exfoliated matrix material.The achievement of making in this field of melting intercalation method at present is few; But commercially produce existing report; For example the Claytone APA organo montmorillonite and the PET that produce of human U.S. Southern Clay company such as Maxfield carries out fusion intercalation; Obtain the intercal type matrix material, but complex process, the cost height gathers.
Summary of the invention
The objective of the invention is to; Can not satisfy the request for utilization problem of heparin tube, liquid drink to existing PET barrier; A kind of preparation method of PET-organic intercalation montmorillonite composite material is provided, can accesses the PET goods good to the vapour lock separating performance water with easy technology.
In order to address the above problem, the present invention adopts following technical scheme:
A kind of preparation method of PET-organic intercalation montmorillonite composite material comprises the steps:
1) the organic intercalation polynite that Yong quaternary alkylphosphonium salt or silane coupling agent and sodium-based montmorillonite intercalation is obtained and the PET of thorough drying mix by 20: 80～80: 20 weight ratio; Obtain mixture, this mixture is processed the PET masterbatch that contains the polynite of machine transplanting of rice layer;
2) the PET masterbatch and the PET that contain the polynite of machine transplanting of rice layer that step 1) are made mix, and make that the mass percent of polynite is 1%-10% in the mixture, use the injection moulding machine injection moulding then, obtain goods.
Preferably, in the step 1), said quaternary alkylphosphonium salt is 12～octadecyl trialkyl halogenation phosphonium salt.
Preferably, said silane coupling agent is γ-An Bingjisanyiyangjiguiwan and analogue or NH
2(CH
2)
3Si (OCH
2CH
3)
3
Preferably, the exchange capacity of said organic intercalation polynite is more than the 90mmol/00 gram.
Preferably; In the step 1), mixture is pressed into sheet at 250 ℃～280 ℃ temperature counterdie, is ground into particulate state with kibbler; Use parallel dual-screw extruding machine melt blending, granulation under 245 ℃～300 ℃ temperature again, obtain containing the PET masterbatch of machine transplanting of rice layer polynite.
Preferably, in the step 1), mixture is mixed with plasticator or Banbury mixer, after the above banburying of PET fusing point, take out cooling, pulverize granulation, obtain containing the PET masterbatch of machine transplanting of rice layer polynite with kibbler.
Preferably, containing the quality percentage composition that organism in the PET masterbatch of machine transplanting of rice layer polynite accounts for the intercalation polynite is 10%～50%.
Preferably, said 12～octadecyl trialkyl halogenation phosphonium salt is 12～octadecyl trimethylammonium bromination phosphonium salt, 12～octadecyl tributyl bromination phosphonium salt, 12～octadecyl, three phenyl phosphonium bromide salt, 12～octadecyl, three first base chlorination phosphonium salts, 12～octadecyl tributyl chlorination phosphonium salt, 12～octadecyl triphenyl phosphonium chloride salt.
Preferably, step 2) in, the PET masterbatch and the PET that contain the polynite of machine transplanting of rice layer mix back dry 4h～8h under 120 ℃～180 ℃ temperature earlier, use the injection moulding machine moulding again.
Preferably, step 2) in, under 265 ℃～330 ℃ temperature, use the injection moulding machine moulding.
Different with the method for modifying of prior art; Sodium-based montmorillonite and PET blend Jiang quaternary alkylphosphonium salt or the modification of silane coupling agent organic intercalation of the present invention; Process the PET masterbatch that contains the polynite of machine transplanting of rice layer earlier; Sneak into pure PET then by a certain percentage and be injection molded into goods, thereby a kind of new Technology that is suitable for scale operation is provided, can access PET goods water and gas excellent in barrier property.
The present invention does not change injection moulding complete processing, the service performance of original PET pipe (comprising heparin tube) goods, and the product that obtains can be used for heparin tube, Beer Bottle, and cosmetics containers such as scent flask, these need in the good container of barrier property.
The present invention can adopt the working process parameter identical with existing PET in being processed into the finished product process; Even under 330 ℃ temperature condition, the organic intercalation polynite of quaternary alkylphosphonium salt or the modification of silane coupling agent organic intercalation is not decomposed yet, and filler 12-hexadecyl quaternary ammonium salts MMT commonly used just has decomposition at 240 ℃ in the prior art; The PET processing temperature is above 290 ℃ even 300 ℃; Quaternary ammonium salt takes place to decompose blackout, and influences the quality of finished product, thereby; The present invention still can adopt the working process parameter identical with existing PET, work simplification in the processed finished products process.
The present invention is because the organic intercalation polynite preparation technology who uses amplifies conveniently, and efficient is high, compares with the technology that needs blend additive or coating in the prior art, can realize scale operation, does not influence production efficiency, and cost is relatively low.
The present invention compares with technologies such as prior art floating coat, in-situ inserted composite algorithm and polymer melt graft process, can realize large-scale production, and the method for filling owing to the employing masterbatch in the technological process, thereby need not disperse to use organic solvent, no environmental protection pressure.
Embodiment
In order to make those skilled in the art understand technical scheme of the present invention better, through specific embodiment the present invention is done further detailed description below.
Embodiment one
1) hexadecyl tributyl phosphonium bromide intercalation sodium-based montmorillonite and PET are pressed into sheet by 20: 80 (W/W) at 265 ℃ temperature counterdie; Be ground into particulate state with kibbler then; Under 265 ℃ temperature, dissolve molten blend, granulation with parallel dual-screw extruding machine again, obtain containing the PET master batch material of 20% (W/W) hexadecyl tributyl phosphonium bromide intercalation polynite, wherein; The exchange capacity 90mmol/100 gram of polynite, organic content 20% in the intercalation polynite;
2) be 2% by the quality percentage composition of setting polynite in the end article; The PET masterbatch and the PET that will contain the polynite of above-mentioned quaternary alkylphosphonium salt intercalation mix; Then at 120 ℃ of following dry 4h, under 265 ℃ with injection moulding machine on injection moulding obtain organic imvite modified PET plastic sheet.
Through check, the content 1.75% of polynite in the plastic sheet that obtains, transmittance surpasses 75% at visible region, is 90% of pure PET; Final OTR oxygen transmission rate reduces about 25%; Permeability rate reduces by 40%.The present invention can be used for preparing the heparin tube of good barrier property.
In the present embodiment; Select hexadecyl tributyl phosphonium bromide intercalation sodium-based montmorillonite for use; In other embodiments, also can select 12～octadecyl trimethylammonium phosphonium bromide intercalation sodium-based montmorillonite or 12～octadecyl, three phenyl phosphonium bromide intercalation sodium-based montmorillonites or 12～octadecyl, three first base phosphonium chloride intercalation sodium-based montmorillonites, 12～octadecyl triphenyl phosphonium chloride intercalation sodium-based montmorillonite, 12～octadecyl tributyl phosphonium chloride intercalation sodium-based montmorillonite for use.
Embodiment two
1) with KH550 (also being γ-An Bingjisanyiyangjiguiwan) intercalation sodium-based montmorillonite and PET by 20: 80 (W/W) on Banbury mixer or forcing machine 275 ℃ mix; Be ground into the PET master batch material that obtains high montmorillonoid-containing behind the pellet; Wherein, The exchange capacity 90mmol/100 gram of polynite, organic content 15% in the intercalation polynite;
2) be 3% polynite by setting ultimate density, PET masterbatch and the PET that will contain the polynite of KH550 intercalation mix, and at 150 ℃ times dry 6h, obtain organic MMT modified plastics sheet extruding on injection moulding machine under 300 ℃ then.
Through check, the final polynite content of the plastic sheet that present embodiment obtains is 2.5%, and transmittance surpasses 80% at visible region, is more than 90% of pure PET; Final OTR oxygen transmission rate reduces about 35%; Permeability rate reduces by 60%.This technology can be used for preparing heparin tube, Beer Bottle and the makeup container containing raw material of good barrier property.
Embodiment three
1) with KH550 intercalation sodium-based montmorillonite and PET by 60: 40 (W/W) on Banbury mixer or forcing machine 275 ℃ mix, banburying; Then take out cooling; Be ground into the PET master batch material that obtains high montmorillonoid-containing behind the pellet with kibbler; Wherein, the exchange capacity 90mmol/100 of polynite gram, organic content is 15% in the intercalation polynite;
2) be 4% polynite by setting ultimate density, the PET masterbatch that will contain the polynite of KH550 intercalation mixes with PET, then at 170 ℃ times dry 8h, obtains organic MMT modified plastics sheet extruding on injection moulding machine under 330 ℃ then.
Through check, the final polynite content of the plastic sheet that present embodiment obtains is 3.5%, and transmittance surpasses 82% at visible region, is more than 91% of pure PET; Final OTR oxygen transmission rate reduces about 32%; Permeability rate reduces by 60%.This technology can be used for preparing heparin tube, Beer Bottle and the makeup container containing raw material of good barrier property.
More than the present invention has been carried out detailed introduction, use concrete example in the literary composition principle of the present invention and embodiment set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of a PET-organic intercalation montmorillonite composite material is characterized in that, comprises the steps:
1) the organic intercalation polynite that Yong quaternary alkylphosphonium salt or silane coupling agent and sodium-based montmorillonite intercalation is obtained and the PET of thorough drying mix by 20: 80～80: 20 weight ratio; Obtain mixture, this mixture is processed the PET masterbatch that contains the polynite of machine transplanting of rice layer;
2) the PET masterbatch and the PET that contain the polynite of machine transplanting of rice layer that step 1) are made mix, and make that the mass percent of polynite is 1%-10% in the mixture, use the injection moulding machine injection moulding then, obtain goods.
2. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 1 is characterized in that, in the step 1), said quaternary alkylphosphonium salt is 12～octadecyl trialkyl halogenation phosphonium salt.
3. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 1 is characterized in that, said silane coupling agent is γ-An Bingjisanyiyangjiguiwan and analogue or NH
2(CH
2)
3Si (OCH
2CH
3)
3
4. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 1 is characterized in that, the exchange capacity of said organic intercalation polynite is more than the 90mmol/100 gram.
5. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 1; It is characterized in that; In the step 1), mixture is pressed into sheet at 250 ℃～280 ℃ temperature counterdie, is ground into particulate state with kibbler; Use parallel dual-screw extruding machine melt blending, granulation under 245 ℃～300 ℃ temperature again, obtain containing the PET masterbatch of machine transplanting of rice layer polynite.
6. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 1; It is characterized in that; In the step 1), mixture is mixed with plasticator or Banbury mixer, after the above banburying of PET fusing point, take out cooling; Pulverize granulation with kibbler, obtain containing the PET masterbatch of machine transplanting of rice layer polynite.
7. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 1 is characterized in that, containing the quality percentage composition that organism in the PET masterbatch of machine transplanting of rice layer polynite accounts for the intercalation polynite is 10%～50%.
8. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 2; It is characterized in that said 12～octadecyl trialkyl halogenation phosphonium salt is 12～octadecyl trimethylammonium bromination phosphonium salt, 12～octadecyl tributyl bromination phosphonium salt, 12～octadecyl, three phenyl phosphonium bromide salt, 12～octadecyl, three first base chlorination phosphonium salts, 12～octadecyl tributyl chlorination phosphonium salt, 12～octadecyl triphenyl phosphonium chloride salt.
9. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 1; It is characterized in that; Step 2) in, the PET masterbatch and the PET that contain the polynite of machine transplanting of rice layer mix back dry 4h～8h under 120 ℃～180 ℃ temperature earlier, use the injection moulding machine moulding again.
10. the preparation method of PET-organic intercalation montmorillonite composite material as claimed in claim 1 is characterized in that step 2) in, under 265 ℃～330 ℃ temperature, use the injection moulding machine moulding.
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Cited By (8)
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| CN103834150A (en) * | 2014-03-12 | 2014-06-04 | 北京崇高纳米科技有限公司 | Material composition for producing beer bottle and production method of bear bottle |
| CN109233247A (en) * | 2018-09-20 | 2019-01-18 | 吕莉 | A kind of preparation method of beer bottle material |
| CN112652844A (en) * | 2020-12-24 | 2021-04-13 | 界首市天鸿新材料股份有限公司 | Power lithium battery flexible packaging film |
| CN112980162A (en) * | 2021-03-19 | 2021-06-18 | 西南科技大学 | Montmorillonite modified PET high-temperature-resistant optical polyester material and preparation method thereof |
| CN115011082A (en) * | 2022-06-10 | 2022-09-06 | 湖北合聚新材料有限公司 | Thin film material and preparation method thereof |
| CN115536997A (en) * | 2022-10-17 | 2022-12-30 | 杭州恒峰塑料制品有限公司 | Blending type barrier plastic packaging container |
| KR102594469B1 (en) * | 2022-12-23 | 2023-10-26 | (주)삼양패키징 | Masterbatch composition comprising pet resin and inorganic particles, pet resin composition comprising the masterbatch composition, and molded article comprising the resin composition |
| CN116948547A (en) * | 2023-06-15 | 2023-10-27 | 宁波勤邦新材料科技股份有限公司 | Novel white reinforced photovoltaic backboard base film, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103834150A (en) * | 2014-03-12 | 2014-06-04 | 北京崇高纳米科技有限公司 | Material composition for producing beer bottle and production method of bear bottle |
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| CN112652844A (en) * | 2020-12-24 | 2021-04-13 | 界首市天鸿新材料股份有限公司 | Power lithium battery flexible packaging film |
| CN112980162A (en) * | 2021-03-19 | 2021-06-18 | 西南科技大学 | Montmorillonite modified PET high-temperature-resistant optical polyester material and preparation method thereof |
| CN112980162B (en) * | 2021-03-19 | 2022-04-15 | 西南科技大学 | Montmorillonite modified PET high-temperature-resistant optical polyester material and preparation method thereof |
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| CN116948547A (en) * | 2023-06-15 | 2023-10-27 | 宁波勤邦新材料科技股份有限公司 | Novel white reinforced photovoltaic backboard base film, preparation method and application thereof |
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Application publication date: 20120502 |