CN101654563B - Crystalline polymer blend and molding product thereof - Google Patents
Crystalline polymer blend and molding product thereof Download PDFInfo
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- CN101654563B CN101654563B CN2008101245299A CN200810124529A CN101654563B CN 101654563 B CN101654563 B CN 101654563B CN 2008101245299 A CN2008101245299 A CN 2008101245299A CN 200810124529 A CN200810124529 A CN 200810124529A CN 101654563 B CN101654563 B CN 101654563B
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Abstract
The invention discloses a crystalline polymer blend. The blend is prepared from 100 portions of crystalline polymer and 0.1 to 10 portions of compound X with the following general formula, wherein A or B is hydrogen, acetoxy, propionyloxy, carbonyl acetoxy, amino acetoxy, 2-amino-propionyloxy, 2-hydroxyl-propionyloxy, acetic acid carbethoxy, carbonyl, phenyl, phenylethyl or benzyl respectively. The blend solves the problem that the application of the crystalline polymer is limited because of low heat resistant temperature. A nucleating agent capable of improving the crystallization of the crystalline polymer is added so as to prepare the crystalline polymer blend with higher melting crystallization temperature and higher crystallization velocity.
Description
Technical field
The present invention relates to a kind of blend of forming by crystalline polymer and nucleator, and the moulded products that obtains by this blend.
Background technology
In recent years, the consumption as the Vilaterm of food, beverage-container, pallet etc. and commodity external packing box material, Vestolen PP 7052, polyester, nylon etc. increases year by year.What accompany therewith is that the amount of using the back waste is also in continuous increase.Because the burning of these wastes and burying has brought various environmental problems.In order to address these problems, in recent years, can to carry out biolytic polymkeric substance and constantly be used.Wherein, biodegradable polyesters, particularly POLYACTIC ACID have received widely in recent years and having gazed at owing to have relative high melt point and relative higher mechanical properties.
And; Enhancing along with the surging of oil price and people's environmental consciousness; With seeding corn and other crops rather than oil; As the synthetic and next POLYACTIC ACID of raw material, be in the field at center in agricultural aquatic products, civil engineering work, packing, container, daily necessities, health care, with the application that has more and more widely.For example,, POLYACTIC ACID need have certain hot patience when being applied to food, beverage-container, pallet etc. and commodity external packing box at least, to prevent distortion that encased conveying or heating are brought and opaque etc.But the heat resisting temperature of biodegradable polyesters that with the POLYACTIC ACID is representative is lower, is example with the POLYACTIC ACID, and heat resisting temperature is no more than 60 ℃, after POLYACTIC ACID is processed the moulding article, uses in case surpass this temperature, will softening transform, thus influenced practical application.
But the crystallization velocity of POLYACTIC ACID own is slower, need improve crystallization velocity through adding nucleator.Add general nucleator such as talcum powder, lime carbonate etc.,, can cause the remarkable decline of the transparency though can improve the crystallization velocity of POLYACTIC ACID.Only add mineral filler in addition, can not guarantee sufficient hot patience.Therefore, again the someone propose in moulding/improve the thermotolerance of POLYACTIC ACID through heat treated way after the moulding.Though POLYACTIC ACID has crystal structure, crystallization is slow.If use the technological forming identical with ordinary resin, the moulding article are also keeping noncrystalline state, and mechanical property and thermotolerance all can not meet the demands.
A kind of heat-resistance polylactic acid window membrane through the two-way stretch preparation has been proposed in Japanese Patent 2000-008349.The crystalline polylactic acid membrane has certain thermotolerance through two-way stretch.But the two-way stretch method can't prepare thicker film/sheet material.And the production of biaxial stretching film needs huge equipment and factory building investment.Further, biaxial stretching film is because partially or completely crystallization is not easy to post forming.
In Japanese Patent H05-504471, propose injection molding behind POLYACTIC ACID mixing talcum powder, the moulding article have higher heat resisting temperature, but add the transparency that a spot of talcum powder also can influence POLYACTIC ACID greatly.And in Japanese Patent H08-193165, talcum powder etc. is added in the POLYACTIC ACID as nucleator, when injection molding, actual crystallization velocity is slower, and product is more crisp.
A kind of poly (lactic acid) composition that contains phenolic antioxidant and amides has been described in Chinese patent CN1539880A; When injection molding; The die temperature of shaper is arranged between the fusion-crystallization starting temperature and glass transition temp of this poly (lactic acid) composition, realizes stable on heating raising through the fusion-crystallization of POLYACTIC ACID in the control moulding article.Yet because POLYACTIC ACID and fusion-crystallization process slowly thereof, amides is difficult to the fusion-crystallization in the independent control POLYACTIC ACID moulding process, must through add talcum powder further improve POLYACTIC ACID crystallization velocity, shorten crystallization time.Therefore, prepared moulding article, when improving hot patience, the transparency can not be controlled effectively.
Summary of the invention
The objective of the invention is to obtain a kind of crystalline polymer blend thereby can improve the crystalline nucleator of crystalline polymer with crystallization velocity of higher melt crystallization temperature and Geng Gao through increase in order to overcome the problem of crystalline polymer because of the low limited use system of heat resisting temperature.
Another object of the present invention provides a kind of moulding article by above-mentioned crystalline polymer blend preparation.
The object of the invention can reach through following measure:
A kind of crystalline polymer blend, form by the component of following weight part:
100 parts of crystalline polymers,
0.1～10 part of compounds X with following general formula,
Wherein, A or B are respectively hydrogen, acetoxyl, propionyloxy, oxyacetic acid base, Padil base, 2-amino-propionyloxy, 2-hydroxyl-propionyloxy, methylol, ethyl acetate base, carbonyl, phenyl, styroyl or benzyl; Be preferably hydrogen, acidic group, propionyloxy, oxyacetic acid base, Padil base, 2-amino-propionyloxy, 2-hydroxyl-propionyloxy, methylol or ethyl acetate base; Further preferred A and B are group inequality, and promptly compounds X has chiral structure, and its raceme or optically active isomer all can be applicable to the present invention.
Crystalline polymer among the present invention can be a polymkeric substance known, that have crystal structure: like polyamide polymers such as polyester such as polyolefinss such as Vestolen PP 7052, polyethyleneterephthalate, nylon; The present invention preferably adopts the crystallinity petchem.
For the crystallinity polyester, mainly be meant crystalline polymer with at least more than one ester group, can be the straight chain shape, also can be dendritic.The crystallinity polyester preferably do not use petroleum resources, can natural degradation, can through natural resource manufacturings such as corn, reduce Carbon emission to prevent aliphatics biodegradable polyesters global warming, that have certain thermotolerance, formability.The aliphatics biodegradable polyesters can be to gather alpha hydroxy acid, gather beta-hydroxy fatty acid, gather ω-hydroxy fatty acid, gather dicarboxylicacid alkylidene group diester etc., preferred POLYACTIC ACID, gathers alpha hydroxy acid etc.Various biodegradable polyesters can be through the known method preparation.Specifically, can prepare by alcohol acid polycondensation, diprotic acid and methods such as diacidic base polycondensation or cyclic monomer ring-opening polymerization.For POLYACTIC ACID, can obtain by the lactic acid direct polymerization or by the rac-Lactide ring-opening polymerization.
As most preferred POLYACTIC ACID in the crystalline polymer of the present invention; Its fusing point is 120～185 ℃; Weight-average molecular weight is 20,000～800,000; As principal constituent, can be the blend of blend, polylactic acid stereoscopic composite (stereocomplex), polylactic acid stereoscopic composite and the POLYACTIC ACID homopolymer and/or the copolymer of poly lactic acid of POLYACTIC ACID homopolymer, copolymer of poly lactic acid, POLYACTIC ACID homopolymer and copolymer of poly lactic acid with L-lactic acid and/or D-lactic acid.The formation mol ratio of L-lactic acid units and D-lactic acid units has no particular limits, and can in 100/0～0/100 scope, select.But in order to guarantee the fusing point of POLYACTIC ACID, any content in preferred L-lactic acid units and the D-lactic acid units is more than 90mol%.
But the polymkeric substance among the present invention, the crystalline polymer of being mentioned above not being confined to can also contain one or more of crystallinity such as Mierocrystalline cellulose, protein, polypeptide, amino acid and verivate thereof or non crystallized other biological degradable components.
The blend method of the crystalline polymer blend described in the present invention can be melt blending, mechanical blending etc. or their combination.Can realize through machineries such as high-speed mixer, single screw extrusion machine, twin screw extruder, Banbury mixeies.
Moulding article of the present invention can be the extrusion molding articles with certain thermotolerance and transparency that described crystalline polymer blend is obtained through fusion, moulding, injection-molded article, flow casting molding article.Thereby and can through in the moulding and/or the moulding post-heat-treated be the thermotolerance that the further crystallization of goods further improves goods.
The invention provides and a kind ofly compare, have the crystalline polymer blend of the crystallization velocity of higher melt crystallization temperature and Geng Gao, have the good transparency and thermotolerance simultaneously through the prepared moulding article of this blend with the matrix crystalline polymer.
Embodiment
Thermal property:
Use the DSC Q100 of TA company, measure Tc.Downcut about 10mg to the film that suppresses with blade, preparation appearance dish.Nitrogen flow is 50ml/min, at room temperature reaches balance, and temperature rise rate is 20 ℃/min, is warmed up to 200 ℃, reads exothermic peak as cold crystallization temperature (T
Cc), endotherm(ic)peak is as fusing point (T
m), eliminated thermal history in 3 minutes at 200 ℃ of constant temperature, rate of cooling is 3 ℃/min, cools to room temperature, reads endotherm(ic)peak as melt crystallization temperature (T
Mc, at room temperature constant temperature is 2 minutes, heats up with 20 ℃/min once more, reads glass transition temp (T
g).
Embodiment 1
With POLYACTIC ACID (4032D; Natureworks), DL-3-indyl-2-amino-propionic acid (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:1) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 120.0 ℃.
Embodiment 2
With POLYACTIC ACID (4032D; Natureworks), DL-3-indyl-2-amino-propionic acid 0.02g totally 2.006 the gram (Tokyo HuaCheng Industry Co., Ltd) (weight ratio is 100:0.3) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 105.7 ℃.
Embodiment 3
With POLYACTIC ACID (4032D; Natureworks), DL-3-indyl-2-amino-propionic acid (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:9) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 125.7 ℃.
Embodiment 4
With POLYACTIC ACID (4032D; Natureworks), D-3-indyl-2-amino-propionic acid (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:1) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 106.2 ℃.
Embodiment 5
With POLYACTIC ACID (4032D; Natureworks), L-3-indyl-2-amino-propionic acid (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:1) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 100.3 ℃.
Embodiment 6
With POLYACTIC ACID (4032D; Natureworks), indyl-2-acetate (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:1) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 98.7 ℃.
Embodiment 7
With POLYACTIC ACID (4032D; Natureworks), indyl-2-acetate (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:1) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 102.7 ℃.
Embodiment 8
With POLYACTIC ACID (4032D; Natureworks), 3-indyl-methyl alcohol (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:1) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 96.4 ℃.
Embodiment 9
With POLYACTIC ACID (4032D; Natureworks), indyl-2-ETHYLE ACETATE (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:1) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 98.7 ℃.
Embodiment 10
With POLYACTIC ACID (4032D; Natureworks), 3-indyl propionic acid (Tokyo HuaCheng Industry Co., Ltd) 0.02g totally 2.02 the gram (weight ratio is 100:1) put into the beaker that fills the 50ml chloroform; Stir after three hours; Solution is poured in the aluminium box, and after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The melt crystallization temperature T that the sample of gained obtains through the DSC test
McIt is 101.7 ℃.
Embodiment 11
With POLYACTIC ACID (4032D; Natureworks), DL-3-indyl-2-amino-propionic acid (Tokyo HuaCheng Industry Co., Ltd) is according to the weight ratio of 100:1; After twin screw extruder (TECHNOVEL) fusion, use casting film machine (Japan company) casting film.The melt crystallization temperature T that the casting films of gained obtains through the DSC test
McIt is 105.6 ℃.
Comparative example 1
With POLYACTIC ACID (4032D, Natureworks) 2g stirred after three hours, and solution is poured in the aluminium box, after one night of air seasoning, Air drying is 2 hours in vacuum drying oven.The sample of gained is tested less than melt crystallization temperature T through DSC
Mc
Claims (7)
1. crystalline polymer blend, it is characterized in that: this blend is made up of the component of following weight part:
100 parts of crystalline polymers,
0.1～10 part of compounds X with following general formula,
Wherein, A or B are respectively hydrogen, acetoxyl, propionyloxy, Padil base, 2-amino-propionyloxy, ethyl acetate base or methylol.
2. blend according to claim 1 is characterized in that: described A and B are group inequality.
3. blend according to claim 2 is characterized in that: described compounds X is raceme or optically active isomer.
4. blend according to claim 1 is characterized in that: described crystalline polymer is POLYACTIC ACID, gathers alpha hydroxy acid, gathers beta-hydroxy fatty acid, gathers ω-hydroxy fatty acid or gather dicarboxylicacid alkylidene group diester.
5. blend according to claim 4 is characterized in that: described crystalline polymer is a POLYACTIC ACID.
6. moulding article that made by blend as claimed in claim 1 is characterized in that: adopt flow casting molding, calendering formation, injection moulding, blow molding or hot press molding method with described blend fusion aftershaping.
7. moulding article according to claim 6 is characterized in that: described moulding article in moulding or moulding after bakingout process.
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| CN2008101245299A CN101654563B (en) | 2008-08-22 | 2008-08-22 | Crystalline polymer blend and molding product thereof |
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| CN2008101245299A CN101654563B (en) | 2008-08-22 | 2008-08-22 | Crystalline polymer blend and molding product thereof |
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| CN101654563A CN101654563A (en) | 2010-02-24 |
| CN101654563B true CN101654563B (en) | 2012-08-08 |
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| CN109054171B (en) * | 2018-06-28 | 2021-09-14 | 广东炜林纳新材料科技股份有限公司 | Polypropylene toughening nucleating agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639235A (en) * | 2002-03-06 | 2005-07-13 | 尤尼吉可株式会社 | Polylactic acid molding and process for producing the same |
| CN1764695A (en) * | 2003-02-04 | 2006-04-26 | 索尼株式会社 | Resin composition and process for producing resin molding |
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2008
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639235A (en) * | 2002-03-06 | 2005-07-13 | 尤尼吉可株式会社 | Polylactic acid molding and process for producing the same |
| CN1764695A (en) * | 2003-02-04 | 2006-04-26 | 索尼株式会社 | Resin composition and process for producing resin molding |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2004-99477A 2004.04.02 |
| JP特开2008-31375A 2008.02.14 |
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