CN103589125A - Polylactic acid/polypropylene blend and preparation method thereof - Google Patents
Polylactic acid/polypropylene blend and preparation method thereof Download PDFInfo
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- CN103589125A CN103589125A CN201310610549.8A CN201310610549A CN103589125A CN 103589125 A CN103589125 A CN 103589125A CN 201310610549 A CN201310610549 A CN 201310610549A CN 103589125 A CN103589125 A CN 103589125A
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Abstract
The invention discloses a polylactic acid/polypropylene blend and a preparation method thereof. The preparation method allows the polylactic acid/polypropylene blend to be prepared through melt blending of polylactic acid, polypropylene, carboxylated polypropylene, diisocyanate, a catalyst, a nucleating agent and an antioxidant by an extruder. The preparation method has the advantages of simplicity and low cost, and the prepared polylactic acid/polypropylene blend has the advantages of good compatibility, excellent mechanical properties and good heat resistance.
Description
Technical field
The present invention relates to a kind of poly(lactic acid)/polypropylene blend and preparation method thereof; Belong to polymer blending modification field.
Background technology
Poly(lactic acid) (PLA) belongs to new polyester material, from the viewpoint of environmental protection, researchs and develops biodegradable material and has become very urgent.The synthetic technology of poly(lactic acid) is ripe gradually at present, and the transparency of poly(lactic acid) is high, can be degradable, be expected to substitute the materials such as polyethylene, polypropylene, polystyrene, and in fields such as agricultural, fiber, wrapping material, automotive interior materials, be used widely.But because poly(lactic acid) hardness is large, easily embrittlement, shock resistance is poor, to thermally labile, expensive, thereby in use range, be subject to certain limitation, its R&D work is becoming study hotspot.In order to reduce mechanical property and the processing characteristics of polluting or improving PLA material, and reduce product cost, people are doing much work aspect PLA blending and modifying.Adopt poly(lactic acid)/polypropene blended can reduce polyacrylic consumption and reduce environmental pollution, can make again product keep good mechanical property.But the consistency of the PLA of polarity and nonpolar polypropylene (PP) is poor, thus need to carry out modification to polypropylene, and add effective compatilizer to carry out blend to PP and PLA, just can reach the consistency that improves both, the blend polymer that processability is superior.
Chinese patent application 200980101536.X discloses a kind of compatible polypropylene and poly(lactic acid) blend and preparation method thereof and using method, adopt a kind of composition that comprises the blend of polyolefine, poly(lactic acid) and reactive modifier, by polypropylene, poly(lactic acid) and reactive modifier reactivity, extrude and form compatible polymer blend.Wherein make polyolefine, polyfunctional acrylic ester comonomer and initiator under applicable condition, form epoxide function polyolefine preparation feedback properties-correcting agent.The method is extruded and is prepared the consistency that compatilizer can improve polypropylene and poly(lactic acid) by reaction, but in blend, chief component is polyolefine, and because preparation process is reacted and extruded at twice, residual acrylate monomer has a certain impact to the performance of product simultaneously.
Chinese patent application 200910212776.9 discloses the preparation method of the polylactic acid modified polypropylene material of a kind of use, adopts a kind of simple method to carry out modification to polypropylene surface, obtains specific biocompatibility, plays the effect of surperficial antiblocking.Polypropylene thin skin is placed in to chromic acid solution heated oxide, then reacts under catalyst action with lactic acid, can obtain novel hernia repairing composite material.The method adopts chemical process that poly(lactic acid) is grafted to polypropylene surface, but because percentage of grafting is lower, while using as matrix material, consistency can be not ideal, and material property can be lower.
United States Patent (USP) 8362145B2 discloses a kind of compatibilized polypropylene/polylactic acid blend and preparation method thereof, this matrix material is comprised of polyolefine, poly(lactic acid) and expanding material, first polyolefine and polyfunctional group Acrylic Acid Monomer are extruded to generation expanding material by reaction, the expanding material generating joins in the mixture of polyolefine and poly(lactic acid), by extruding and being orientated, can prepare high performance thin film.Because the percentage of grafting of expanding material is not high enough, and expanding material and polyolefinic consistency are better, still not ideal with the consistency of poly(lactic acid), preparation process needs proceed step by step to improve the price of goods, and the reason of these aspects has limited the application of this patent of invention.
The preparation of poly(lactic acid)/polypropylene blend and the patent report of application aspect are less, but adopt poly(lactic acid)/polypropene blended can reduce polyacrylic consumption and reduce environmental pollution, because poly(lactic acid) and the nonpolar polyacrylic consistency of polarity are poor.
Summary of the invention
The present invention is directed to poly(lactic acid)/polypropylene blend material of the prior art and exist over-all properties poor, the defect that production cost is higher, is limited to its application, object is to provide a kind of cost low, consistency is good, and mechanical property is excellent, the poly(lactic acid)/polypropylene blend of good heat resistance.
Another object of the present invention is to be to provide that a kind of technique is simple, cost is low, the method for the described poly(lactic acid)/polypropylene blend of preparation of safety and environmental protection.
The invention provides a kind of poly(lactic acid)/polypropylene blend, this poly(lactic acid)/polypropylene blend is prepared by melt blending by following mass parts component:
60～95 parts of poly(lactic acid);
7～23 parts of polypropylene;
5～20 parts of carboxylation polypropylene;
1～7 part of vulcabond;
0.05～0.35 part of catalyzer;
0.1～3 part of nucleator;
0.1～0.5 part, oxidation inhibitor.
Described polylactic acid molecule amount is 0.8 * 10
5～2.0 * 10
5.
Described polypropylene molecule amount is 1.4 * 10
5～8.6 * 10
5.
Described carboxylation polypropylene is one or more in carboxylated polypropylene, acrylic acid-grafted polypropylene, methacrylic acid graft polypropylene, maleic anhydride inoculated polypropylene.
The percentage of grafting of described carboxylation polypropylene carboxyl is 0.8～1.0%, and temperature be 190 ℃, load for the melting index of testing under the condition of 2.16kg be 30～100g/10min.
Described vulcabond is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.
Described catalyzer is stannous octoate and/or tin protochloride.
Described nucleator is multiamide nucleating agent in polylactic acid production, TMC-306(nucleating agent in polylactic acid production), TMC-328(nucleating agent in polylactic acid production) in one or more.
Described oxidation inhibitor is one or more in three-(nonyl phenyl) phosphorous acid esters, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, hydroxyl pentaerythritol ester, the positive octadecanol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid etc.
The present invention also provides a kind of preparation method of described poly(lactic acid)/polypropylene blend, this preparation method is after polylactic acid slice, polypropylene, carboxylation polypropylene, vulcabond, catalyzer, nucleator and oxidation inhibitor are joined and disperseed in high-speed mixer, by twin screw extruder at 180～210 ℃ melt blending, extrude, cut into slices, obtain the section of poly(lactic acid)/polypropylene blend.
Beneficial effect of the present invention: the present invention successfully comes blending and modifying poly(lactic acid) to obtain the good poly(lactic acid)/polypropylene blend of consistency with cheap polypropylene, greatly improve the over-all properties of poly(lactic acid)/polypropylene blend, and effectively reduced the cost of poly(lactic acid)/polypropylene blend.The present invention adds a certain amount of carboxylation polypropylene and vulcabond in the composition of raw materials of poly(lactic acid)/polypropylene blend, they have generated poly(lactic acid) and the polyacrylic graft copolymer of carboxylation in melt blending process, this graft copolymer with the good nonpolar segment of polypropylene compatible and the good polarity segment of poly(lactic acid) consistency, effectively increased the consistency of whole poly(lactic acid)/polypropylene blend, its mechanical property, thermotolerance, mobility and rub resistance are all effectively improved; Preparation method of the present invention is simple, and raw material is cheap, low for equipment requirements, greatly reduces production cost, is easy to suitability for industrialized production.
Embodiment
Following examples are intended to further illustrate the present invention, rather than restriction the scope of protection of the invention.
In following examples 1～4, polylactic acid molecule amount is about 1.0 * 10
5; Polypropylene molecule amount is about 5 * 10
5; The percentage of grafting of the carboxylation polypropylene carboxyl adopting is about 0.9%, and is that the melting index of testing under 190 ℃, the load condition that is 2.16kg is about 60g/10min in temperature.
Embodiment 1
By polylactic acid slice vacuum-drying to moisture content, be 30～150ppm; By 80.2 parts of polylactic acid slice, 9 parts of polypropylene, 7 parts of carboxylated polypropylene, 3 parts of diphenylmethanediisocyanates, 0.3 part of stannous octoate, 0.3 part of nucleator TMC-306; Oxidation inhibitor 0.2 part (parts by weight) joins in high-speed mixer, and high speed dispersion obtained poly(lactic acid)/polypropylene miser after 5 minutes; By mixed uniformly mixture by twin screw extruder at 200 ℃ melt blending, extrude, cutting into slices makes poly(lactic acid)/polypropylene blend and cuts into slices.
Embodiment 2
By polylactic acid slice vacuum-drying to moisture content, be 30～150ppm; By 75.3 parts of polylactic acid slice, 13 parts of polypropylene, 9 parts of carboxylated polypropylene, 2 parts of hexamethylene diisocyanates, 0.2 part of stannous octoate, 0.3 part of nucleator TMC-328; Oxidation inhibitor 0.2 part (parts by weight) joins in high-speed mixer, and high speed dispersion obtained poly(lactic acid)/polypropylene miser after 5 minutes; By mixed uniformly polydactyl acid mixture by twin screw extruder at 190 ℃ melt blending, extrude, cutting into slices makes poly(lactic acid)/polypropylene blend and cuts into slices.
Embodiment 3
By polylactic acid slice vacuum-drying to moisture content, be 30～150ppm; By 80.2 parts of polylactic acid slice, 9 parts of polypropylene, 7 parts of acrylic acid-grafted polypropylenes, 2 parts of hexamethylene diisocyanates, 0.3 part of stannous octoate, 0.3 part of nucleator TMC-306; Oxidation inhibitor 0.2 part (parts by weight) joins in high-speed mixer, and high speed dispersion obtained poly(lactic acid)/polypropylene miser after 5 minutes; By mixed uniformly mixture by twin screw extruder at 190 ℃ melt blending, extrude, cutting into slices makes poly(lactic acid)/polypropylene blend and cuts into slices.
Embodiment 4
By polylactic acid slice vacuum-drying to moisture content, be 30～150ppm; By 75.3 parts of polylactic acid slice, 13 parts of polypropylene, 9 parts of maleic anhydride inoculated polypropylenes, 3 parts of diphenylmethanediisocyanates, 0.2 part of stannous octoate, 0.3 part of nucleator TMC-328; Oxidation inhibitor 0.2 part (parts by weight) joins in high-speed mixer, and high speed dispersion obtained poly(lactic acid)/polypropylene miser after 5 minutes; By mixed uniformly polydactyl acid mixture by twin screw extruder at 200 ℃ melt blending, extrude, cutting into slices makes poly(lactic acid)/polypropylene blend and cuts into slices.
Wherein the melting index of the prepared poly(lactic acid)/polypropylene blend of embodiment 1～4 detects according to GB/T1043-93 according to GB/T9341-2000, shock strength according to GB/T1040-1992, modulus in flexure according to GB/T1633-2000, tensile strength according to GB/T3682-2000, vicat softening point temperature, and its performance perameter is as shown in table 1.
The performance of table 1 poly(lactic acid)/polypropylene blend
Claims (10)
1. poly(lactic acid)/polypropylene blend, is characterized in that, by following mass parts component, by melt blending, is prepared:
60～95 parts of poly(lactic acid);
7～23 parts of polypropylene;
5～20 parts of carboxylation polypropylene;
1～7 part of vulcabond;
0.05～0.35 part of catalyzer;
0.1～3 part of nucleator;
0.1～0.5 part, oxidation inhibitor.
2. poly(lactic acid)/polypropylene blend according to claim 1, is characterized in that, described polylactic acid molecule amount is 0.8 * 10
5～2.0 * 10
5.
3. poly(lactic acid)/polypropylene blend according to claim 1, is characterized in that, described polypropylene molecule amount is 1.4 * 10
5～8.6 * 10
5.
4. poly(lactic acid)/polypropylene blend according to claim 1, is characterized in that, described carboxylation polypropylene is one or more in carboxylated polypropylene, acrylic acid-grafted polypropylene, methacrylic acid graft polypropylene, maleic anhydride inoculated polypropylene.
5. poly(lactic acid)/polypropylene blend according to claim 4, it is characterized in that, the percentage of grafting of described carboxylation polypropylene carboxyl is 0.8～1.0%, and temperature be 190 ℃, load for the melting index of testing under the condition of 2.16kg be 30～100g/10min.
6. poly(lactic acid)/polypropylene blend according to claim 1, it is characterized in that, described vulcabond is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.
7. poly(lactic acid)/polypropylene blend according to claim 1, is characterized in that, described catalyzer is stannous octoate and/or tin protochloride.
8. poly(lactic acid)/polypropylene blend according to claim 1, is characterized in that, described nucleator is one or more in multiamide nucleating agent in polylactic acid production, TMC-306, TMC-328.
9. poly(lactic acid)/polypropylene blend according to claim 1, it is characterized in that, described oxidation inhibitor is three-(nonyl phenyl) phosphorous acid esters, tricresyl phosphite (2,4-di-tert-butyl-phenyl) one or more in ester, hydroxyl pentaerythritol ester, the positive octadecanol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid.
10. the preparation method of the poly(lactic acid)/polypropylene blend as described in claim 1～9 any one, it is characterized in that, after polylactic acid slice, polypropylene, carboxylation polypropylene, vulcabond, catalyzer, nucleator and oxidation inhibitor are joined and are disperseed in high-speed mixer, by twin screw extruder at 180～210 ℃ melt blending, extrude, cut into slices, obtain the section of poly(lactic acid)/polypropylene blend.
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| CN104927320A (en) * | 2015-05-25 | 2015-09-23 | 华南农业大学 | Bamboo fiber reinforced polylactic acid composite material used for 3D printing and preparation method for bamboo fiber reinforced polylactic acid composite material |
| CN105623213A (en) * | 2014-11-30 | 2016-06-01 | 黑龙江鑫达企业集团有限公司 | Preparation method of high-toughness and high-fluidity polylactic acid/polypropylene alloy |
| CN107033567A (en) * | 2017-05-16 | 2017-08-11 | 广州找塑料新材料科技有限公司 | Peanut shell powder filled polypropylene lactic acid composite material and preparation method thereof |
| CN107043524A (en) * | 2017-05-22 | 2017-08-15 | 安徽三义和能源科技有限公司 | A kind of disposable plastic product composite polylactic acid resin |
| CN107057307A (en) * | 2017-05-22 | 2017-08-18 | 安徽三义和能源科技有限公司 | A kind of ageing-resistant environmentally friendly composite polylactic acid plastics |
| CN107090166A (en) * | 2017-06-08 | 2017-08-25 | 四川新升塑胶实业有限公司 | A kind of environmentally-friendly plastic bottle |
| CN109294185A (en) * | 2018-09-10 | 2019-02-01 | 武汉金发科技有限公司 | A kind of automotive bumper material and the preparation method and application thereof |
| CN114316424A (en) * | 2021-11-22 | 2022-04-12 | 金发科技股份有限公司 | Transparent weather-resistant PP/PS composite material and preparation method thereof |
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| CN104927320A (en) * | 2015-05-25 | 2015-09-23 | 华南农业大学 | Bamboo fiber reinforced polylactic acid composite material used for 3D printing and preparation method for bamboo fiber reinforced polylactic acid composite material |
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| CN107090166A (en) * | 2017-06-08 | 2017-08-25 | 四川新升塑胶实业有限公司 | A kind of environmentally-friendly plastic bottle |
| CN109294185A (en) * | 2018-09-10 | 2019-02-01 | 武汉金发科技有限公司 | A kind of automotive bumper material and the preparation method and application thereof |
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| CN114316424A (en) * | 2021-11-22 | 2022-04-12 | 金发科技股份有限公司 | Transparent weather-resistant PP/PS composite material and preparation method thereof |
| CN114316424B (en) * | 2021-11-22 | 2023-08-25 | 金发科技股份有限公司 | Transparent weather-proof PP/PS composite material and preparation method thereof |
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