CN102108194A - Polylactic acid/fatty dibasic acid and diol polyester composite - Google Patents
Polylactic acid/fatty dibasic acid and diol polyester composite Download PDFInfo
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Abstract
The invention discloses a polylactic acid/fatty dibasic acid and diol polyester composite, which mainly comprises 40 to 98 weight parts of polylactic resin, 10 to 50 weight parts of fatty dibasic acid and diol polyester, 10 to 30 weight parts of plasticizer, 0.1 to 2 weight parts of capping agent, 0.1 to 2 weight parts of crosslinking agent and 0.01 to 0.1 weight part of crosslinking catalyst. The composite disclosed by the invention has higher mechanical performance and high impact strength, can completely degrade and can be used to make lunch boxes, plastic bags, agricultural thin films, food and medical packages, automobile interior ornaments and other products, and has a bright application prospect.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of poly(lactic acid)/aliphatic diacid diol polyester composition, be specifically related to the poly(lactic acid) aliphatic diacid diol polyester composition with excellent mechanical properties of a kind of plasticizer-containing, end-capping reagent, linking agent, crosslinking catalyst.
Background technology
Plastics a bit are widely used so that its light weight, intensity height, good endurance, painted and forming process are easy etc.But because the harm that the good endurance of plastics has also caused plastic refuse that environment is caused, the conventional plastic waste can't decompose in physical environment, thereby makes rivers, ocean, soil be subjected to grievous injury, and becomes serious social concern gradually.For this reason, the research that utilizes the Biodegradable material that microorganism in the water or in the soil can decompose, be formed, can not polluted environment by occurring in nature material capable of circulation is day by day become the emphasis of concern.
Poly(lactic acid) is the polymkeric substance that obtains for the main raw material polymerization with lactic acid, and raw material sources fully and can regenerate.The production process of poly(lactic acid) is pollution-free, and product can biological degradation, is implemented in the circulation of occurring in nature, is the ideal green macromolecular material therefore.Yet poly(lactic acid) causes product frangible, easily broken because of the mechanical property of its goods is not strong.In order to address this problem, the macromolecular material with soft character is used to and polylactic acid blend or copolymerization.
Polymer, Vol.35,2233 (1994) disclose the technology of a kind of polyhydroxycarboxyliacid acid and polycaprolactone blend, but because the consistency of its molecular scale is poor, can make material become soft though the content of polycaprolactone increases, thermotolerance can obviously descend, and mechanical property is not good.
U.S. Pat P5202413 discloses the blend of a kind of poly(lactic acid) and aliphatic diacid diol polymer, because the molecular weight of polyester is lower, can't be met the blend of flexibility, physical strength, thermotolerance, forming process.
The Japanese Patent spy opens the multipolymer that clear 63-145661 discloses a kind of poly(lactic acid) and polycaprolactone, and the flexibility of this multipolymer is better, but thermotolerance is not good, and opaque, and physical strength is low, it is used be restricted.
Japanese patent laid-open 9-95603 discloses the blend of a kind of poly(lactic acid), aliphatic diacid diol polyester, chainextender, utilize chainextender to improve the molecular weight of goods, thereby obtain mechanical property and flexibility preferably, simultaneously, by adding sequestrant the metal complex that contains in its chainextender is lost activity, prolong the work-ing life of product, still, the reaction efficiency of chainextender is lower, and the lifting of physical strength is limited.
Summary of the invention
The objective of the invention is to address the above problem, a kind of soft poly(lactic acid) with superior mechanical intensity/aliphatic diacid diol polyester composition of biodegradable is provided.
The present invention is achieved by the following scheme:
A kind of poly(lactic acid)/aliphatic diacid diol polyester composition, said composition contains following ingredients:
Polylactic resin (A) 10～98 weight parts; Aliphatic diacid diol polyester (B) 1～90 weight part; Softening agent (C) 1～50 weight part; End-capping reagent (D) 0.01～5 weight part; Linking agent (E) 0.01～5 weight part; Crosslinking catalyst (F) 0.001～0.5 weight part.
Poly(lactic acid) belongs to bio-based materials by the lactic acid polymerizes that amylofermentation forms, and the content that increases the poly(lactic acid) composition helps to reduce Carbon emission; Plasticizer loading is less than 10 weight parts, and may soft effect to occur not obvious, then causes cost to rise greater than 30 weight parts; End-capping reagent is less than that 0.1 weight part, linking agent are less than 0.1 weight part, crosslinking catalyst content is less than the situation that DeGrain may appear in 0.01 weight part, crosses to cause molecular weight too high at most processing difficulties.Therefore, above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition preferably mainly contains following ingredients: polylactic resin (A) 40～98 weight parts; Aliphatic diacid diol polyester (B) 10～50 weight parts; Softening agent (C) 10～30 weight parts; End-capping reagent (D) 0.1～2 weight part; Linking agent (E) 0.1～2 weight part; Crosslinking catalyst (F) 0.01～0.1 weight part.
Poly(lactic acid) of the present invention/aliphatic diacid diol polyester composition is except above-mentioned main component, still can add other known additive, for example, thermo-stabilizer, antioxidant, photostabilizer, lubricant, tinting material, various mineral filler, fire retardant, crystallization nucleating agent, opening agent.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described poly(lactic acid) is poly (l-lactic acid), poly-D-lactic acid or poly-DL-lactic acid or both above blends; Perhaps poly (l-lactic acid) gathers both above multipolymers in D-lactic acid, the poly-DL-lactic acid; Perhaps poly (l-lactic acid), the blend of both above multipolymers in poly-D-lactic acid, the poly-DL-lactic acid.The weight-average molecular weight of this polylactic resin is 5～50w.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described aliphatic diacid diol polyester (B) is one or both in poly butylene succinate or the poly-succinic acid-butanediol adipic acid ester.Wherein the weight-average molecular weight of poly butylene succinate and poly-succinic acid-butanediol adipic acid ester is 5～50w.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described softening agent (C) is one or more in citric acid ester plasticizer, polyalcohols derivative softening agent, fatty acid ester plasticiser or the Reoplex.
Above-mentioned citric acid ester plasticizer is one or more in triethyl citrate, tri-n-butyl citrate, Triethyl citrate acetate, the positive butyl ester of citric acid acetyl three, acetyl tributyl citrate three (the 2-ethyl the is own) ester; in view of cost and market popularity, optimization citric acid tri-n-butyl.
Polyalcohols derivative softening agent is a diethylene glycol dibenzoate, triethylene glycol dibenzoate, triglycol two (2 Ethylbutanoic acid) ester, triglycol (2 ethyl hexanoic acid) ester, triethylene glycol dieaprylate, Tetraglycol 99 two (2 ethyl hexanoic acid) ester, diethylene glycol dipelargonate, triethylene glycol dipelargonate, triethylene glycol diheptylate, the di-alcohol diacetate esters, triethylene-glycol diacetate, glyceryl monoacetate, glyceryl diacetate, triacetin, tributyrin, in the glycerin tripropionate one or more, in view of cost and market popularity, the preferably glycerine triacetate, tributyrin, in the glycerin tripropionate one or more, more preferably tributyrin.
Fatty acid ester plasticiser is the acetyl methyl ricinoleate; acetyl ricinoleic acid butyl ester; single ricinoleic acid glyceryl ester; single ricinoleic acid glycol ether ester; glycerine three (acetyl ricinoleic acid) ester; single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks; methyl ricinoleate; the ricinoleic acid butyl ester; single ricinoleic acid propylene glycol ester; ethanoyl ricinoleic acid methoxyl group ethyl ester; Wickenol 111; iso-octyl palmitate; Isopropyl myristate; n-butyl myristate; the tetradecanoic acid Wickenol 111; eight acetate sucrose esters; sucrose benzoate; the dibenzoic acid monooctyl ester; the tall oil acid methyl esters; the different monooctyl ester of tall oil acid; methyl abietate; hydrogenated methyl abietate; hydroabietyl alcohol; 2; 2; 4-trimethylammonium-1; 3 pentanediol diisobutyrates; diisodecyl glutarate; dibutoxyethyl glutarate; didecyl glutarate; pentanedioic acid two (butoxy oxyethyl group second) ester; Zerol; glyceryl monooleate; glycerine list linolenate; Glyceryl monobehenate; sorbitan mono-laurate; the anhydrous sorbitol monopalmitate; sorbitan monostearate; the anhydrous sorbitol tristearate; sorbitan monooleate; in the Witconol AL 69-66 one or more; in view of cost and market popularity; preferred single ricinoleic acid glyceryl ester; single ricinoleic acid glycol ether ester; glycerine three (acetyl ricinoleic acid) ester; single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks; the tetradecanoic acid Wickenol 111; the different monooctyl ester of tall oil acid; hydrogenated methyl abietate; Zerol; glyceryl monooleate; glycerine list linolenate; the anhydrous sorbitol tristearate; in the Witconol AL 69-66 one or more, more preferably single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks; Zerol; in the anhydrous sorbitol tristearate one or more.
Reoplex is that molecular weight is that 3000～20000 polyoxyethylene glycol, molecular weight are 800～8000 poly-hexanodioic acid-1,3-fourth diester, molecular weight are 800～8000 poly-hexanodioic acid-1, and 4-fourth diester, molecular weight are that 800～8000 poly-pentanedioic acid diester in the last of the ten Heavenly stems, molecular weight are one or more in 800～8000 the poly-suberic acid second diester.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described end-capping reagent (D) for the compound of Ju You oxazoline functional group, have carbodiimide functionality compound, have isocyanate functional group's compound＞, wherein be preferably compound with carbodiimide functionality, further preferred Stabaxol1LF, Stabaxol P, LA-1, HMV-8CA, DCC (N, N '-dicyclohexylcarbodiimide).
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described linking agent (E) is the compound that Ju You oxazoline palace can be rolled into a ball, compound with multi-functional epoxy's group, compound with isocyanate functional group, wherein be preferably compound with multi-functional epoxy's group, further preferred epoxy equivalent (weight) is the compound with multi-functional epoxy's group of 5～5000g/mol, epoxy equivalent (weight) cross low can cause excessively crosslinked, processibility descends, the too high meeting of epoxy equivalent (weight) causes cross-linking effect not obvious, and therefore more preferably epoxy equivalent (weight) is the compound with multi-functional epoxy's group of 50～500g/mol.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described crosslinking catalyst (F) is one or more in metal salts of organic acids, the metal complex.
Above-mentioned metal salts of organic acids is that backbone structure is an alkane, alkene, the monobasic of aromatic hydrocarbon or polycarboxylic acid and potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, plumbous, lithium, manganese, in the metal salts of organic acids that cobalt or barium metal ion form one or more, preferred backbone structure is an alkane, alkene, the monobasic of aromatic hydrocarbon or polycarboxylic acid and magnesium, zinc, in the metal salts of organic acids that iron or barium metal ion form one or more, more preferably Magnesium Stearate, Zinic stearas, iron stearate, barium stearate, magnesium oleate, zinc oleate, iron oleate, barium oleate, magnesium benzoate, Zinc dibenzoate, phenylformic acid iron, Barium dibenzoate, magnesium citrate, zinc citrate, ironic citrate, barium citrate, terephthalic acid magnesium, terephthalic acid zinc, in terephthalic acid iron or the terephthalic acid barium one or more, further preferred Zinic stearas, barium stearate, in the zinc citrate one or more.
Metal complex is one or more in the complex compound formed of acetylacetonate compound and potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, lead, lithium, manganese, cobalt or barium metallic element, in preferred magnesium acetylacetonate, zinc acetylacetonate, ferric acetyl acetonade or the acetylacetone barium one or more, more preferably zinc acetylacetonate.
With above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition melt blending after overmolding processing makes the moulding product of poly (lactic acid) composition.The forming process means can adopt conventional extruding, injection moulding, foaming, blowing, curtain coating, mold pressing etc.
Be significantly improved via poly(lactic acid) of the present invention/aliphatic diacid diol polyester composition physical strength, this advantage obviously improves confirmation by the mold pressing sample shock strength of composition.The simple molecular weight of linking agent raising goods and then the method for raising physical strength used can only make the Charpy shock strength of goods reach 150～200kJ/m
2, and the poly(lactic acid) among the present invention/aliphatic diacid diol polyester composition is tested its shock strength through similarity condition and can be reached 300kJ/m
2More than.The moulding product of poly(lactic acid) of the present invention/aliphatic diacid diol polyester composition can be made products such as cutlery box, plastics bag, agricultural film, food medical packaging, automotive trim, are with a wide range of applications.
Embodiment
For further specifying purpose of the present invention, feature and advantage, illustrated below by specific embodiment.
Extruding pelletization:
Under vacuum environment, with dry 5 hours of poly(lactic acid) particle.By prescription various raw materials are carried out melt blending by twin screw extruder and extrude, melt generates composition mother particle through tank cooling back, 180 ℃ of forcing machine feed zone temperature, and second section 190 ℃, all the other sections are 200 ℃.
Compression molding:
With composition mother particle under 80 ℃, vacuum environment dry 5 hours, by vulcanizing press master batch is pressed into the thick diaphragm of 0.2mm, plate temperature is 200 ℃ on the vulcanizing press, 200 ℃ of following plate temperatures, sample melted 3 minutes, exhaust 3 times, exhaust pressure 10～12MPa, pressurize 30 seconds, dwell pressure 10MPa.
Shock strength is measured:
The sample diaphragm is made the batten of 5mm * 50mm, test its shock strength, pendulum energy 1J, initial angle 135 degree by the Charpy shock-testing machine.Each sample test seven times is averaged behind the removal maximin.
The raw material that embodiment, Comparative Examples are used:
(1) polylactic resin (A)
A-1:Natural Works makes 4032D, weight-average molecular weight 18～22w.
A-2:Natural Works makes 6251D, weight-average molecular weight 7～13w.
A-3: the system REVODE 101 of the positive biotech firm in sea, weight-average molecular weight 10w.
(2) aliphatic diacid diol polyester (B)
B-1: clear and polymer system PBSA, trade mark 3001G, weight-average molecular weight 15～20W.
B-2: the system PBS of Mitsubishi Chemical, trade mark AZ91T, weight-average molecular weight 15～20W.
B-3: prosperous rich medicine company system PBS, trade mark 1803F, weight-average molecular weight 15～20W.
B-4: and Xinghua worker makes PBS, trade mark film-grade, weight-average molecular weight 15～20W.
(3) softening agent (C)
C-1: traditional Chinese medicines reagent system tri-n-butyl citrate.
C-2:Eastman Chem system glycerine tri-n-butyl.
C-3:Danisco system single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks.
C-4: ancient cooking vessel additive system Zerol in the Zhangjiagang.
C-5:Danisco system anhydrous sorbitol tristearate.
C-6: traditional Chinese medicines reagent system cetomacrogol 1000 0.
(4) end-capping reagent (D)
D-1: Lay mattress chemistry system Stabaxol 1LF.
D-2: day clear spinning LA-1.
D-3: day clear spinning HMV-8CA.
D-4: Shanghai covalent chemical system DCC.
(5) linking agent (E)
E-1: lean worker that refines in Beijing makes TGIC, epoxy equivalent (weight) 99g/mol.
E-2:BASF system Joncryl ADR-4368, epoxy equivalent (weight) 285g/mol.
E-3:BASF system Joncryl ADR-4380, epoxy equivalent (weight) 450g/mol.
(6) crosslinking catalyst (F)
F-1: traditional Chinese medicines reagent system Zinic stearas.
F-2: traditional Chinese medicines reagent system barium stearate.
F-3: traditional Chinese medicines reagent system zinc citrate.
F-4: traditional Chinese medicines reagent system zinc acetylacetonate.
Embodiment 1～3, Comparative Examples 1 (the every weight part of following examples is 100 grams)
Table 1
Embodiment 4～6, Comparative Examples 2.
Table 2
Embodiment 7～9, Comparative Examples 3.
Table 3
Embodiment 10～12, Comparative Examples 4.
Table 4
Embodiment 13～15, Comparative Examples 5.
Table 5
Embodiment 16,17, Comparative Examples 6,7.
Table 6
Claims (11)
1. poly(lactic acid)/aliphatic diacid diol polyester composition is characterized in that said composition contains following ingredients:
Polylactic resin (A) 10～98 weight parts; Aliphatic diacid diol polyester (B) 1～90 weight part; Softening agent (C) 1～50 weight part; End-capping reagent (D) 0.01～5 weight part; Linking agent (E) 0.01～5 weight part; Crosslinking catalyst (F) 0.001～0.5 weight part; Wherein, softening agent (C) is one or more in citric acid ester plasticizer, polyalcohols derivative softening agent, fatty acid ester plasticiser or the Reoplex.
2. poly(lactic acid) according to claim 1/aliphatic diacid diol polyester composition is characterized in that said composition contains following ingredients:
Polylactic resin (A) 40～98 weight parts; Aliphatic diacid diol polyester (B) 10～50 weight parts; Softening agent (C) 10～30 weight parts; End-capping reagent (D) 0.1～2 weight part; Linking agent (E) 0.1～2 weight part; Crosslinking catalyst (F) 0.01～0.1 weight part.
3. poly(lactic acid) according to claim 1 and 2/aliphatic diacid diol polyester composition is characterized in that, described aliphatic diacid diol polyester (B) is one or both in poly butylene succinate or the poly-succinic acid-butanediol adipic acid ester.
4. poly(lactic acid) according to claim 1/aliphatic diacid diol polyester composition, it is characterized in that described citric acid ester plasticizer is one or more in triethyl citrate, tri-n-butyl citrate, Triethyl citrate acetate, the positive butyl ester of citric acid acetyl three, acetyl tributyl citrate three (the 2-ethyl the is own) ester; Described polyalcohols derivative softening agent is a diethylene glycol dibenzoate, triethylene glycol dibenzoate, triglycol two (2 Ethylbutanoic acid) ester, triglycol (2 ethyl hexanoic acid) ester, triethylene glycol dieaprylate, Tetraglycol 99 two (2 ethyl hexanoic acid) ester, diethylene glycol dipelargonate, triethylene glycol dipelargonate, triethylene glycol diheptylate, the di-alcohol diacetate esters, triethylene-glycol diacetate, glyceryl monoacetate, glyceryl diacetate, triacetin, tributyrin, in the glycerin tripropionate one or more; Described fatty acid ester plasticiser is the acetyl methyl ricinoleate, acetyl ricinoleic acid butyl ester, single ricinoleic acid glyceryl ester, single ricinoleic acid glycol ether ester, glycerine three (acetyl ricinoleic acid) ester, single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks, methyl ricinoleate, the ricinoleic acid butyl ester, single ricinoleic acid propylene glycol ester, ethanoyl ricinoleic acid methoxyl group ethyl ester, Wickenol 111, iso-octyl palmitate, Isopropyl myristate, n-butyl myristate, the tetradecanoic acid Wickenol 111, eight acetate sucrose esters, sucrose benzoate, the dibenzoic acid monooctyl ester, the tall oil acid methyl esters, the different monooctyl ester of tall oil acid, methyl abietate, hydrogenated methyl abietate, hydroabietyl alcohol, 2,2,4-trimethylammonium-1,3 pentanediol diisobutyrate, diisodecyl glutarate, dibutoxyethyl glutarate, didecyl glutarate, pentanedioic acid two (butoxy oxyethyl group second) ester, Zerol, glyceryl monooleate, glycerine list linolenate, Glyceryl monobehenate, sorbitan mono-laurate, the anhydrous sorbitol monopalmitate, sorbitan monostearate, the anhydrous sorbitol tristearate, sorbitan monooleate, in the Witconol AL 69-66 one or more; Described Reoplex is that molecular weight is that 3000～20000 polyoxyethylene glycol, molecular weight are 800～8000 poly-hexanodioic acid-1,3-fourth diester, molecular weight are 800～8000 poly-hexanodioic acid-1, and 4-fourth diester, molecular weight are that 800～8000 poly-pentanedioic acid diester in the last of the ten Heavenly stems, molecular weight are one or more in 800～8000 the poly-suberic acid second diester.
5. poly(lactic acid) according to claim 1 and 2/aliphatic diacid diol polyester composition is characterized in that, the compound of described end-capping reagent (D) for having carbodiimide functionality.
6. poly(lactic acid) according to claim 1 and 2/aliphatic diacid diol polyester composition, it is characterized in that, described linking agent (E) is for having the compound of multi-functional epoxy's group, and wherein, the epoxy equivalent (weight) with compound of multi-functional epoxy's group is 5～5000g/mol.
7. poly(lactic acid) according to claim 1 and 2/aliphatic diacid diol polyester composition is characterized in that, described crosslinking catalyst (F) is one or more in metal salts of organic acids, the metal complex.
8. poly(lactic acid) according to claim 7/aliphatic diacid diol polyester composition, it is characterized in that described metal salts of organic acids is that backbone structure is one or more in the metal salts of organic acids that forms of the monobasic of alkane, alkene, aromatic hydrocarbon or polycarboxylic acid and potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, lead, lithium, manganese, cobalt or barium metal ion.
9. poly(lactic acid) according to claim 8/aliphatic diacid diol polyester composition, it is characterized in that described metal salts of organic acids is one or more in Magnesium Stearate, Zinic stearas, iron stearate, barium stearate, magnesium oleate, zinc oleate, iron oleate, barium oleate, magnesium benzoate, Zinc dibenzoate, phenylformic acid iron, Barium dibenzoate, magnesium citrate, zinc citrate, ironic citrate, barium citrate, terephthalic acid magnesium, terephthalic acid zinc, terephthalic acid iron or the terephthalic acid barium.
10. poly(lactic acid) according to claim 7/aliphatic diacid diol polyester composition, it is characterized in that described metal complex is one or more in the complex compound formed of acetylacetonate compound and potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, lead, lithium, manganese, cobalt or barium metallic element.
11. poly(lactic acid) according to claim 10/aliphatic diacid diol polyester composition is characterized in that described metal complex is one or more in magnesium acetylacetonate, zinc acetylacetonate, ferric acetyl acetonade or the acetylacetone barium.
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| CN104220534A (en) * | 2012-04-09 | 2014-12-17 | 乐金华奥斯有限公司 | Biodegradable resin composition containing eco-friendly plasticizer, and biodegradable resin product using same |
| CN103819884A (en) * | 2012-11-16 | 2014-05-28 | 上海载和实业投资有限公司 | Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof |
| CN105086969A (en) * | 2015-07-13 | 2015-11-25 | 中国石油大学(北京) | Degradable resin material for operation of oil and gas field and preparation method thereof |
| CN105802155A (en) * | 2016-05-12 | 2016-07-27 | 江西禾尔斯环保科技有限公司 | Preparation method and application of PBAT modified material |
| CN106380856A (en) * | 2016-09-29 | 2017-02-08 | 东至绿洲环保化工有限公司 | Organic silicon plasticizer capable of reducing fracture rate of agricultural films |
| CN112409647A (en) * | 2020-10-16 | 2021-02-26 | 安徽省怀宁县希望纸塑有限责任公司 | Biodegradable material for preparing tableware and preparation method thereof |
| CN115028899A (en) * | 2022-04-18 | 2022-09-09 | 高邮市恒昌泡沫制品有限公司 | Degradable environment-friendly antibacterial tableware and preparation process thereof |
| CN115044179A (en) * | 2022-06-15 | 2022-09-13 | 贵州省材料产业技术研究院 | Plasticized polylactic acid composite material and preparation method thereof |
| CN115044179B (en) * | 2022-06-15 | 2024-07-16 | 贵州省材料产业技术研究院 | Plasticized polylactic acid composite material and preparation method thereof |
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