CN102627842B - Preparation method of halogen-free and flame-retardant polylactic acid composite material - Google Patents
Preparation method of halogen-free and flame-retardant polylactic acid composite material Download PDFInfo
- Publication number
- CN102627842B CN102627842B CN 201210115534 CN201210115534A CN102627842B CN 102627842 B CN102627842 B CN 102627842B CN 201210115534 CN201210115534 CN 201210115534 CN 201210115534 A CN201210115534 A CN 201210115534A CN 102627842 B CN102627842 B CN 102627842B
- Authority
- CN
- China
- Prior art keywords
- composite material
- polylactic acid
- halogen
- poly
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of a halogen-free and flame-retardant polylactic acid composite material. The method comprises the following steps of: feeding a polylactic acid composition into a screw extruder; fusing and compounding to obtain a blend; extruding and pelletizing; and drying to obtain the polylactic acid composite material. The polylactic acid composition is prepared by mixing the following components in percentage by weight: 30-50 percent of polylactic acid, 30-50 percent of polybutane diacid-co-butylene terephthalate, 5-30 percent of polycaprolactone, 1-5 percent of a nucleating agent and 5-30 percent of silicon nitride, wherein the nucleating agent is a mixed emulsion formed by fully dissolving a disodium salicylate solid into a resin emulsion, wherein the mass ratio of disodium salicylate to the resin emulsion is 1:(1-4). The flame retardance of the prepared polylactic acid composite material can reach the UL94V-0 grade standard, and the mechanical property, surface property, processing performance, coloring performance and the like are improved remarkably. Moreover, the production process is easy to control, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of halogen-free flame retardant polylactic acid composite material.
Background technology
Along with the raising of environmental consciousness, the degradable biological macromolecular material is paid close attention to widely in recent years, and the exploitation of this class material and preparation are also popular at present research topics.Wherein, poly(lactic acid) (also claims polylactide, polylactide, PLA, belong to aliphatic polyester) as a kind of the most typical, application is biodegradable plastic more widely, can be that main raw material carries out the polymerization preparation with lactic acid, raw material sources fully and can regenerate (for example, with corn, cassavas etc. are starting material), the production process of poly(lactic acid) is pollution-free, in physical environment and certain condition and can be broken down into again carbonic acid gas under the time and water return to the nature circle (again joining in the photosynthesis process of plant), realization is in the circulation of occurring in nature, there is good degradability and compostability.In addition, poly(lactic acid) has higher Rigidity and strength, does not need to add the materials such as glass and just can reach general electronics and the needed mechanical property of device such as electric.
The topmost performance factor of restriction poly(lactic acid) application is that its thermotolerance is very poor at present, easily burning.In fact, this is also the total shortcomings of most degradable biological macromolecular materials.Poly(lactic acid) under room temperature generally is vitreous state, with other biodegradated polymer materal, to compare its rigidity better, but its thermotolerance is very poor (for example, 0.45MPa the heat-drawn wire under load is only 55 ℃), its flame retardant properties belongs to the UL94HB level, burning easily, makes the application of poly(lactic acid) be limited by very large.Such as for electronics and the fire-retardant device such as electric, just being subject to difficulty.Therefore, improve flame retardant resistance, the thermotolerance of poly(lactic acid) extremely important for the Application Areas of widening poly(lactic acid).
For improving the performance of poly-lactic acid material, common way is by blending and modifying, improves heat-drawn wire and the moulding processability (demoulding, shortening shaping cycle etc.) of material.In the correlative study of the preparation and modification of poly(lactic acid), thermotolerance aspect: have the people once to propose with CaCO
3, TiO
2and BaSO
4inorganic salt add in poly(lactic acid) as nucleator, but can't realize suitability for industrialized production so far; Also someone adopts talcum powder as nucleator, this is the current nucleator in unique industrial production that can be applied to poly(lactic acid), but talcous particle diameter, content, shape alignment degree etc. are very large to the crystallization nucleation influential effect of poly(lactic acid), cause the more difficult control of industrial production of poly(lactic acid).For example, talcous particle diameter is too little, and the dispersed bad secondary aggregation that causes producing can not be given full play to the effect of crystallization nucleation, and the problem of poor heat resistance can not fully be solved; Particle diameter is too large, and talc particle can become the defect in moulded products again, on physical property or the condition of surface of poly-lactic acid material, can cause bad impact; When content is too low, only generate a small amount of nuclei of crystallization, cause material thermal resistance insufficient, too high levels, easily cause the poly-lactic acid material embrittlement, and physical property is caused to detrimentally affect.In addition, in the industrial production application process, talcous dust can bring harm to operator healthy.Also someone adopts the crystallization nucleating agent that the tetrafluoroethylene based polymer is poly(lactic acid), improve the thermotolerance of poly(lactic acid), yet, viscous deformation (creep) can occur in its goods under the long-time continuous load, also has in addition poor fluidity, processing difficulties, linear expansivity are large, do not degrade under natural condition, and during high temperature, degradation production has the hypertoxic perfluoroisobutylene of minute quantity.PLA, because it has good biocompatibility and degradation property, has been widely used in biomedical sector, but the application of present stage PLA still is restricted, and this is mainly due to the poly(lactic acid) existent defect: property is crisp, and shock resistance is poor; To thermally labile, price.For overcoming above-mentioned shortcoming, must carry out modification to poly(lactic acid), wherein blending and modifying is one of focus of research.The blending and modifying of poly(lactic acid) mainly refers to regulate the proportioning between two components by selecting suitable blend components, improves the consistency of component and adopts the different means such as forming materials working method, can obtain the type material that meets each generic request.The people is arranged at present in the halogen-free flame-proof polylactic acid of research, also not high to the requirement of goods flame retardant rating, mechanical property, surface properties, processing characteristics and tinctorial property.For example, the aluminium hydroxide of halogen-free non-phosphor, flame retardant of magnesium hydroxide, shortcoming is must be very large for reaching good flame retardant effect loading level, about 40-60% (massfraction).Large like this loading level must cause the mobility variation of resin when mixing, moulding and the physical property of products formed to reduce.Adopt the main drawback of phosphorus flame retardant to be: resistance to elevated temperatures is poor.Also someone studies nitrogen system, silicon-series five-retardant polydactyl acid, but the performance of goods is restricted.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of preparation method of improved halogen-free flame retardant polylactic acid composite material is provided.
For solving above technical problem, the present invention takes following technical scheme:
A kind of preparation method of halogen-free flame retardant polylactic acid composite material, it is that poly (lactic acid) composition is fed in screw extrusion press, carry out melting mixing and make blend, extruding pelletization, be drying to obtain described lactic acid composite material, wherein: by weight percentage, described poly (lactic acid) composition is by poly(lactic acid) (PLA) 30%～50%, poly-succinic-altogether-mutual-phenenyl two acid bromide two alcohol ester (PBST) 30%～50%, polycaprolactone (PCL) 5%～30%, nucleator 1%～5% and silicon nitride (Si3N4) 5%～30% mixes, described nucleator is that Whitfield's ointment disodium solid is dissolved in the mixed emulsion formed in resin emulsion fully, wherein, the mass ratio of Whitfield's ointment disodium and resin emulsion is 1: 1～4.
Preferably, as the optical purity of the poly(lactic acid) of raw material, be 80%～99%, the residual lactide amount is total mass 0.05%～1%.The weight-average molecular weight of poly(lactic acid) is between 30,000～100,000.Poly(lactic acid) can be by commercially available, and for example the biological K-2200 model of manufacturing of Jiangsu card card, also can be used the known polymerization process of the public to prepare.
According to an aspect of the present invention, poly-succinic-altogether-mutual-phenenyl two acid bromide two alcohol ester's weight-average molecular weight is between 80,000～130,000, and it can be by commercially available, the SK-600 model that for example Jiangsu card card biology is manufactured.Be used as compatilizer according to polycaprolactone of the present invention, the weight-average molecular weight of polycaprolactone is between 60,000～120,000, it can be by commercially available, GN5066 (state can scientific & technical corporation manufacture) for example, perhaps can also be by 6-caprolactone in the Catalyzed by Organometallic Compounds agent, dihydroxyl or trihydroxy-are ring-opening polymerization preparation under the initiator condition.
According to an aspect of the present invention, described resin emulsion is epoxy resin latex or ester-polyurethane resin emulsion or the combination of the two.Preferably, epoxy resin latex is xylene solvent dilution type epoxy resin latex, and this emulsion median size is 0.1～0.5 μ m, solid content 60%～70%; Ester-polyurethane resin emulsion is aqueous polyurethane resin emulsion, and this emulsion median size is 0.1～0.5 μ m, and solid content is 50%～70%.
Preferably, by weight percentage, described poly (lactic acid) composition is mixed by poly(lactic acid) 30%～40%, poly-succinic-altogether-mutual-phenenyl two acid bromide two alcohol ester 30%～40%, polycaprolactone 5%～15%, nucleator 1%～3% and silicon nitride 15%～25%.
Preferably, in described mixed emulsion, the mass ratio of Whitfield's ointment disodium and resin emulsion is 1: 1～2.
Due to the enforcement of technique scheme, the present invention compared with prior art has following advantage:
It is nucleator that the resin emulsion of Whitfield's ointment disodium is take in the present invention, take silicon nitride as halogen-free flame retardants, and added specific polycaprolactone, poly terephthalic acid-altogether-succinic acid-butanediol ester and prepared lactic acid composite material, prepared lactic acid composite material, except flame retardant resistance can reach the UL94V-0 grade standard, also is significantly increased at aspects such as mechanical property, surface properties, processing characteristics and tinctorial properties.In addition, production process of the present invention is easily controlled, and is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but the invention is not restricted to following examples.
Embodiment 1
The present embodiment provides a kind of preparation method of halogen-free flame retardant polylactic acid composite material, and it comprises the steps:
(1), prepare nucleator: by 500g Whitfield's ointment disodium (card card, 5500 models) solid is poured the 1000g epoxy resin latex into, and (state can, the GN-120 model) in, under room temperature, stir about is 120 minutes, until Whitfield's ointment disodium salt solid dissolves the formation mixed emulsion fully, is nucleator.
(2), melting mixing prepares halogen-free flame retardant polylactic acid composite material: adopt 400g PLA and 400gPBST, the nucleator that 11g step (1) makes, 189g PCL and 100g silicon nitride, after mixing, add twin screw extruder to carry out melting mixing, the following (twin screw extruder of the parameter of melting mixing; Ф=26mm; L/D=40; Intake zone to the temperature in each district of die head is followed successively by: 150 ℃, 180 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 195 ℃, 195 ℃; Pressure 36; Moment of torsion 54%; Feed rate 23s), in 230 ℃ of left and right, make the PLA blend, extruding pelletization then, drying, obtain the lactic acid composite material section.The lactic acid composite material section is carried out to injection molding, and die temperature is 110 ℃, and be 120 seconds cooling time.Sheet material to obtained by molding is tested, and the data of test are referring to table 1.
Embodiment 2
The present embodiment provides a kind of preparation method of halogen-free flame retardant polylactic acid composite material, specific as follows: as to adopt 350g PLA and 350g PBST, 10g nucleator (with embodiment 1), 100g PCL and 200g silicon nitride, after mixing, add twin screw extruder to carry out melting mixing, the following (twin screw extruder of the parameter of melting mixing; Ф=26mm; L/D=40; Intake zone to the temperature in each district of die head is followed successively by: 150 ℃, 180 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 195 ℃, 195 ℃; Pressure 36; Moment of torsion 54%; Feed rate 23s), in 230 ℃ of left and right, make the PLA blend, extruding pelletization then, drying, obtain the lactic acid composite material section.The lactic acid composite material section is carried out to injection molding, and die temperature is 110 ℃, and be 120 seconds cooling time.Sheet material to obtained by molding is tested, and the data of test are referring to table 1.
Comparative Examples 1
This Comparative Examples provides a kind of preparation method of lactic acid composite material, specific as follows: as to adopt 400g PLA and 400g PBST, 10g nucleator (with embodiment 1) and 190g PCL, after mixing, add twin screw extruder to carry out melting mixing, the following (twin screw extruder of the parameter of melting mixing; Ф=26mm; L/D=40; Intake zone to the temperature in each district of die head is followed successively by: 150 ℃, 180 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 195 ℃, 195 ℃; Pressure 36; Moment of torsion 54%; Feed rate 23s), in 230 ℃ of left and right, make the PLA blend, extruding pelletization then, drying, obtain the lactic acid composite material section.The lactic acid composite material section is carried out to injection molding, and die temperature is 110 ℃, and be 120 seconds cooling time.Sheet material to obtained by molding is tested, and the data of test are referring to table 1.
As seen from Table 1, according to embodiments of the invention 1 and 2 and the physicals of Comparative Examples 1 all greatly be better than prior art products.Wherein, the thermotolerance of the lactic acid composite material that the embodiment of the present invention 1 and 2 makes, flame retardant properties are very good, its low load heat-drawn wire can reach respectively 141 ℃ and 139 ℃, has reached and has adopted talcum powder as the resistance toheat level of the currently available products of nucleator and adopt the flame retardant resistance that hydrated metal oxide is the fire retardant polydactyl acid.
The performance data of table 1 lactic acid composite material
Above the present invention is described in detail; its purpose is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. the preparation method of a halogen-free flame retardant polylactic acid composite material, it is that poly (lactic acid) composition is fed in screw extrusion press, carry out melting mixing and make blend, extruding pelletization, be drying to obtain described lactic acid composite material, it is characterized in that: by weight percentage, described poly (lactic acid) composition is by poly(lactic acid) 30% ~ 50%, poly-succinic-altogether-mutual-phenenyl two acid bromide two alcohol ester 30% ~ 50%, polycaprolactone 5% ~ 30%, nucleator 1% ~ 5% and silicon nitride 5% ~ 30% mix, described nucleator is that Whitfield's ointment disodium solid is dissolved in the mixed emulsion formed in resin emulsion fully, wherein, the mass ratio of Whitfield's ointment disodium and resin emulsion is 1:1 ~ 4.
2. the preparation method of halogen-free flame retardant polylactic acid composite material according to claim 1 is characterized in that: the optical purity as the poly(lactic acid) of raw material is 80% ~ 99%, and the residual lactide amount is total mass 0.05% ~ 1%.
3. the preparation method of halogen-free flame retardant polylactic acid composite material according to claim 1, it is characterized in that: the weight-average molecular weight of described poly(lactic acid) is between 30,000 ~ 100,000.
4. the preparation method of halogen-free flame retardant polylactic acid composite material according to claim 1 is characterized in that: described poly-succinic-altogether-mutual-phenenyl two acid bromide two alcohol ester's weight-average molecular weight is between 80,000 ~ 130,000.
5. the preparation method of halogen-free flame retardant polylactic acid composite material according to claim 1, it is characterized in that: the weight-average molecular weight of described polycaprolactone is between 60,000 ~ 120,000.
6. the preparation method of halogen-free flame retardant polylactic acid composite material according to claim 1, it is characterized in that: described resin emulsion is epoxy resin latex or ester-polyurethane resin emulsion or the combination of the two.
7. the preparation method of halogen-free flame retardant polylactic acid composite material according to claim 6, it is characterized in that: described epoxy resin latex is xylene solvent dilution type epoxy resin latex, and this emulsion median size is 0.1 ~ 0.5 μ m, and solid content is 60% ~ 70%.
8. the preparation method of halogen-free flame retardant polylactic acid composite material according to claim 6, it is characterized in that: described ester-polyurethane resin emulsion is aqueous polyurethane resin emulsion, and this emulsion median size is 0.1 ~ 0.5 μ m, and solid content is 50% ~ 70%.
9. the preparation method of halogen-free flame retardant polylactic acid composite material according to claim 6, it is characterized in that: in described mixed emulsion, the mass ratio of Whitfield's ointment disodium and resin emulsion is 1:1 ~ 2.
10. according to the preparation method of the described halogen-free flame retardant polylactic acid composite material of any one claim in claim 1 to 9, it is characterized in that: by weight percentage, described poly (lactic acid) composition is mixed by poly(lactic acid) 30% ~ 40%, poly-succinic-altogether-mutual-phenenyl two acid bromide two alcohol ester 30% ~ 40%, polycaprolactone 5% ~ 15%, nucleator 1% ~ 3% and silicon nitride 15% ~ 25%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210115534 CN102627842B (en) | 2012-04-19 | 2012-04-19 | Preparation method of halogen-free and flame-retardant polylactic acid composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210115534 CN102627842B (en) | 2012-04-19 | 2012-04-19 | Preparation method of halogen-free and flame-retardant polylactic acid composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102627842A CN102627842A (en) | 2012-08-08 |
| CN102627842B true CN102627842B (en) | 2013-04-24 |
Family
ID=46586249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210115534 Expired - Fee Related CN102627842B (en) | 2012-04-19 | 2012-04-19 | Preparation method of halogen-free and flame-retardant polylactic acid composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102627842B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633730A (en) * | 2016-09-27 | 2017-05-10 | 无锡卡卡生物科技有限公司 | Preparation method for degradable flame-retardant polylactic acid composite material |
| GB2591121A (en) * | 2020-01-16 | 2021-07-21 | Floreon Transf Packaging Limited | Polylactic acid flame resistant blend |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007040609A1 (en) * | 2005-09-16 | 2007-04-12 | Pactiv Corporation | Polymer films with treated fillers and products and methods of using same |
| CN101787185B (en) * | 2009-02-06 | 2012-01-18 | 深圳市科聚新材料有限公司 | Heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material and preparation method thereof |
| CN102241879A (en) * | 2011-06-14 | 2011-11-16 | 安徽理工大学 | Flame-retardant biodegradable resin/bamboo fiber composite material and preparation method thereof |
-
2012
- 2012-04-19 CN CN 201210115534 patent/CN102627842B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102627842A (en) | 2012-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103819884A (en) | Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof | |
| CN109401232A (en) | Flame-proof polylactic acid composition and its expanded bead | |
| CN105038158A (en) | Preparation method of food-grade full-degradable high-temperature-resistant polylactic acid composite material | |
| CN101781445B (en) | Intumescent flame retardant polybutylene succinate and preparation method thereof | |
| CN104497365A (en) | Bentonite/ starch composite degrading material produced by melt intercalation and preparation method | |
| CN111171542B (en) | High CTI flame-retardant polycarbonate alloy material and preparation method and application thereof | |
| CN103102646A (en) | Low-melting point and high-crystallization temperature PET copolyester, its preparation method and application | |
| CN105623219A (en) | Full-degradable injection product and preparation method therefor | |
| JP7507153B2 (en) | Resin composition and method for producing same | |
| WO2023044959A1 (en) | All biomass, fully degradable material, preparation method therefor and application thereof | |
| CN102627842B (en) | Preparation method of halogen-free and flame-retardant polylactic acid composite material | |
| WO2023104076A1 (en) | Polycarbonate composition, plastic made of same, and preparation method therefor | |
| CN102206406A (en) | Method for preparing transparent heat-resistance polylactic acid modification material | |
| CN106867246A (en) | It is a kind of to be applied to flame-retardant PA 66 mixed component of monofilament and preparation method thereof | |
| CN102234412A (en) | High-performance flame-retardant polylactic acid/polycarbonate (PLA/PC) alloy | |
| CN103102661B (en) | Rapid nucleating agent for polylactic resin | |
| CN103360681B (en) | Halogen-free flame retardant highlight polypropylene and preparation method thereof | |
| CN104151789A (en) | Low-warping high voltage resistance PBT modified material and preparation method thereof | |
| CN106633730A (en) | Preparation method for degradable flame-retardant polylactic acid composite material | |
| CN102875987B (en) | A kind of organic nucleating agent and its preparation and application | |
| TW202330783A (en) | Biodegradable resin composition comprising high content of calcium carbonate | |
| CN101423625B (en) | Rapid nucleating agent of polylactic resin | |
| CN109777049A (en) | Polybutylene terephthalate (PBT) resin combination | |
| CN103509320B (en) | A kind of halogen-free flame-retardant polycarbonate composition and preparation method thereof | |
| CN103467942B (en) | The biological plastics that PBT and PLA is blended |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120808 Assignee: Wuxi source of Jin Amperex Technology Limited Assignor: Zhangjiagang Chaineng Biological Technology Co., Ltd. Contract record no.: 2015320000304 Denomination of invention: Preparation method of halogen-free and flame-retardant polylactic acid composite material Granted publication date: 20130424 License type: Exclusive License Record date: 20150505 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130424 Termination date: 20170419 |