CN104619745B - The manufacture method of block copolymer - Google Patents
The manufacture method of block copolymer Download PDFInfo
- Publication number
- CN104619745B CN104619745B CN201380046383.XA CN201380046383A CN104619745B CN 104619745 B CN104619745 B CN 104619745B CN 201380046383 A CN201380046383 A CN 201380046383A CN 104619745 B CN104619745 B CN 104619745B
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- CN
- China
- Prior art keywords
- resin
- block copolymer
- polylactic acid
- based resin
- acid based
- Prior art date
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 228
- 239000011347 resin Substances 0.000 claims abstract description 228
- 229920000747 poly(lactic acid) polymer Polymers 0.000 claims abstract description 126
- 239000004626 polylactic acid Substances 0.000 claims abstract description 126
- 150000002148 esters Chemical group 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- -1 halide salts Chemical class 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 13
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (N-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract description 27
- JJTUDXZGHPGLLC-UHFFFAOYSA-N dilactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 abstract description 21
- 238000007792 addition Methods 0.000 description 57
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 18
- 238000002844 melting Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
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- 238000004898 kneading Methods 0.000 description 11
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical group C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000003809 water extraction Methods 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 102100017254 TEX30 Human genes 0.000 description 7
- 101700031485 TEX30 Proteins 0.000 description 7
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- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
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- 238000005660 chlorination reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000004676 glycans Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
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- 239000012298 atmosphere Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
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- 230000000704 physical effect Effects 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N Isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920001451 Polypropylene glycol Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
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- 125000002843 carboxylic acid group Chemical group 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
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- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 238000006011 modification reaction Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229960001735 pentaerythritol Drugs 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000001052 transient Effects 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N β-Propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides the manufacture method of the poly lactic acid series block copolymer that a kind of residual lactide is few.A kind of manufacture method of the block copolymer of polylactic acid based resin and resin (A), it is characterized in that, resin (following, the resin that intramolecular has at least one hydroxyl is referred to as resin (A)) and ester exchange catalyst that polylactic acid based resin, intramolecular have at least one hydroxyl melt at ambient pressure.
Description
Technical field
The present invention relates to the manufacture method of block copolymer, it is characterised in that described block copolymer is by poly lactic acid series
Resin and intramolecular have the resin formation of at least one hydroxyl, as the manufacturing condition of this block copolymer, by polylactic acid
It is that resin, intramolecular have the resin of at least one hydroxyl and ester exchange catalyst melts at ambient pressure.
Background technology
In recent years, due to the raising of environmental consciousness, so the discarded soil contamination problem brought of plastic or plastics
The burning of goods causes carbon dioxide to increase thus causes greenhouse effects of the earth problem to receive publicity.As for the former countermeasure,
Extensively carry out about the Biodegradable resin being completely decomposed into carbon dioxide molecule and hydrone in the environment of in soil
Research, exploitation, as the countermeasure for the latter, even if extensively having carried out about the Material synthesis being derived from biology by plant etc.
Burning also will not be to the research of biomass resin bringing new carbon dioxide to bear in air, exploitation.
As being suitable for both and becoming the present aspect also advantageous resin of ratio, the concern to polylactic acid based resin carries
High.If owing to being used alone polylactic acid based resin, flexibility is not enough, so such as in Farm mulch, shopping bag, packaging
With being wound around in the purposes such as film, stretched film, have studied by using poly lactic acid series copolymer, interpolation plasticizer to carry out softnessization.
Poly lactic acid series block copolymer, by being used alone or mixing with polylactic acid based resin, can be as flexibility
Resin uses.Particularly, in the case of mixing with polylactic acid based resin, block copolymer can play merit as plasticizer
Energy.Such as, the plasticizer formed by polylactic acid-polyether block copolymer described in patent documentation 1, owing to polylactic acid chain segment has
Help to prevent to ooze out, polyether segment contributes to the plasticization of polylactic acid, thus with existing polylactic acid based resin plasticizer phase
Ratio, has the resistance to such feature of exudative excellence.
The manufacture method of these poly lactic acid series block copolymers, as Patent Document 1, usual way is, with molecule
Inside there is the hydroxyl of resin of at least one hydroxyl as starting point, make the i.e. lactide ring-opening polymerisation of cyclic dimer of lactic acid.Make
For other method, as shown in patent documentation 2, it is known that the manufacture method of a kind of poly lactic acid series block copolymer, it is characterised in that make
Polylactic acid based resin and intramolecular have the resin melting of at least one hydroxyl, then add ester exchange catalyst, under reduced pressure
Carry out ester exchange reaction.
Prior art literature
Patent documentation
Patent documentation 1: No. 4363325 publications of Japanese Patent No.
Patent documentation 2: Japanese Unexamined Patent Publication 2004-231773 publication
Summary of the invention
The problem that invention is to be solved
In the lactide ring-opening polymerisation method described in patent documentation 1, there are the following problems: in polymerization, sublimed third hands over
Ester occurs deposition to cause the pollution of reactor, and a unreacted lactide part remains in obtained poly lactic acid series block altogether
In polymers thus cause resin produce lactide stink, hydrolytic resistance deteriorate.It addition, in the method described in patent documentation 2,
Owing under reduced pressure reacting, so promoting because of the intramolecular ester exchange reaction of polylactic acid based resin to generate lactide, from
And produce problem similar to the above.
The present invention solves described existing problem, is derived from manufacturing the side of the few specific block copolymer of residual lactide
Method.
Solve the means of problem
In order to solve above-mentioned problem, the present invention proposes following manufacture method.I.e., as described below.
(1) a kind of polylactic acid based resin is (following, by polylactic acid based resin and resin (A) with the block copolymer of resin (A)
Block copolymer be referred to as block copolymer) manufacture method, it is characterised in that polylactic acid based resin, intramolecular are had to
The resin (following, the resin that intramolecular has at least one hydroxyl is referred to as resin (A)) of a few hydroxyl and ester exchange catalysis
Agent is melted (following, will to melt referred to as normal pressure at ambient pressure and melt operation) at ambient pressure.
(2) according to the manufacture method of the block copolymer described in (1), it is characterised in that described normal pressure melts operation double
Carry out in screw extruder (following, this double screw extruder is referred to as double screw extruder 1).
(3) according to the manufacture method of the block copolymer described in (1) or (2), it is characterised in that described resin (A) is poly-
Aklylene glycol resin.
(4) according to the manufacture method of the block copolymer according to any one of (1)～(3), it is characterised in that described ester is handed over
Catalyst changeout is acylate and/or the halide salts of metal of metal.
(5) manufacture method of the mixture of a kind of polylactic acid based resin and block copolymer, it is characterised in that will pass through
(2) block copolymer of the method manufacture described in is introduced directly in other double screw extruder in double screw extruder 1, with
Polylactic acid based resin mixes.
(6) manufacture method of the mixture of a kind of polylactic acid based resin and block copolymer, it is characterised in that relative to logical
Cross the block copolymer that the method described in (2) manufactures, from the side charging of the same double screw extruder manufacturing this block copolymer
Device puts into polylactic acid based resin, thus in the same double screw extruder manufacturing this block copolymer by this block copolymer and
Polylactic acid based resin mixes.
Invention effect
By using the normal pressure as feature of present invention to melt operation, it is possible to obtain the block copolymerization that remaining lactide is few
Thing.The block copolymer that the present invention is obtained, by being used alone and mixing with polylactic acid based resin, can be as flexibility
Resin use in the molded bodys such as film, can also be work perfectly well as polylactic acid based resin in addition has resistance to exudative increasing
Mould agent to use.
Detailed description of the invention
The present invention is that polylactic acid based resin is (following, by polylactic acid based resin and resin with the block copolymer of resin (A)
(A) block copolymer is referred to as block copolymer) manufacture method, it is characterised in that polylactic acid based resin, intramolecular are had
The resin (following, the resin that intramolecular has at least one hydroxyl is referred to as resin (A)) of at least one hydroxyl and ester exchange
Catalyst is melted (following, will to melt referred to as normal pressure at ambient pressure and melt operation) at ambient pressure.
Below the manufacture method of the block copolymer of the present invention is illustrated.
(polylactic acid based resin)
In the present invention, as the manufacture raw material of block copolymer, use polylactic acid based resin.Polylactic acid based resin is
Refer to, using Pfansteihl unit and/or D-ALPHA-Hydroxypropionic acid unit as the polymer of main composition composition.Here, main composition composition refers to,
In monomeric unit entirety 100mol% in the polymer, the ratio of lactic acid units is the maximum meaning, preferably at whole monomers
In unit 100mol%, lactic acid units is 70～100mol%.
Poly (l-lactic acid) in the present invention refers to, in the whole lactic acid units 100mol% in polymer, Pfansteihl unit
Content ratio is more than 50mol% and at below 100mol%.On the other hand, the poly-D-ALPHA-Hydroxypropionic acid in the present invention refers to, in polymer
Whole lactic acid units 100mol% in, the content ratio of D-ALPHA-Hydroxypropionic acid unit is more than 50mol% and at below 100mol%.
But, the polylactic acid based resin in the present invention does not contains the polylactic acid based resin of block copolymerization resin (A).Separately
Outward, in the case of resin (A) and polylactic acid based resin copolymerization, it is referred to as block copolymer.
For poly (l-lactic acid), according to the content ratio of D-ALPHA-Hydroxypropionic acid unit, the crystallinity of resin self can change.That is,
If the content ratio of D-ALPHA-Hydroxypropionic acid unit increases in poly (l-lactic acid), then the crystallinity step-down of poly (l-lactic acid), close to amorphous, on the contrary
Ground, if the content ratio of D-ALPHA-Hydroxypropionic acid unit reduces in poly (l-lactic acid), then the crystallinity of poly (l-lactic acid) increases.Similarly, for
Poly-D-ALPHA-Hydroxypropionic acid, according to the content ratio of Pfansteihl unit, the crystallinity of resin self can change.If that is, poly-D-ALPHA-Hydroxypropionic acid
The content ratio of middle Pfansteihl unit increases, the crystallinity step-down of the most poly-D-ALPHA-Hydroxypropionic acid, close to amorphous, if on the contrary, poly-D-
In lactic acid, the content ratio of Pfansteihl unit reduces, and the crystallinity of the most poly-D-ALPHA-Hydroxypropionic acid increases.
The content ratio of Pfansteihl unit in poly (l-lactic acid) used in the present invention, or poly-D-ALPHA-Hydroxypropionic acid used in the present invention
The content ratio of middle D-ALPHA-Hydroxypropionic acid unit, can at random regulate.Formed at the block copolymer that the present invention is obtained and need machine
In the case of the molded body of tool intensity, in whole lactic acid units 100mol%, preferably Pfansteihl unit is 90～100mol%, or
Person's D-ALPHA-Hydroxypropionic acid unit is 90～100mol%, and further preferred Pfansteihl unit is 95～100mol%, or D-ALPHA-Hydroxypropionic acid unit is
95～100mol%.It addition, using the plasticising as crystalline polylactic acid system resin of the block copolymer that obtained of the present invention
In the case of agent, form eutectic from the polylactic acid chain segment making polylactic acid based resin and block copolymer and suppress block copolymer
The purpose oozed out is set out, and the content ratio of Pfansteihl and D-ALPHA-Hydroxypropionic acid is the most as described above.On the contrary, the present invention is being obtained
Block copolymer or the block copolymer that obtained containing the present invention as the polylactic acid based resin of plasticizer for the heat of film
In the case of sealing, owing to preferred resin is low-crystalline or amorphism, so in whole lactic acid units 100mol%, Pfansteihl
Unit and D-ALPHA-Hydroxypropionic acid unit are preferably 10～90mol%.
Crystalline polylactic acid system resin in the present invention refers to, this polylactic acid based resin is placed under the heating of 100 DEG C 1
Hour, situation about being then determined with differential scanning calorimeter (DSC) under conditions of the programming rate of 20 DEG C/min
Under, observe the polylactic acid based resin of the crystalline fusion heat being derived from polylactic acid composition.
On the other hand, amorphism polylactic acid based resin alleged in the present invention refers to, is being determined in the same fashion
In the case of, do not show the polylactic acid based resin of fusing point.
Polylactic acid based resin used in the present invention, it is also possible to random copolymerization other monomeric unit in addition to lactic acid.Make
For other monomer, can enumerate, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, ethohexadiol, nonanediol, decanediol,
1,4 cyclohexane dimethanol, neopentyl glycol, glycerol, tetramethylolmethane, bisphenol-A, Polyethylene Glycol, polypropylene glycol and polytetramethylene two
The diol compounds such as alcohol, oxalic acid, adipic acid, decanedioic acid, Azelaic Acid, dodecanedioic acid, malonic acid, 1,3-propanedicarboxylic acid, hexamethylene diformazan
Acid, p-phthalic acid, M-phthalic acid, phthalic acid, naphthalenedicarboxylic acid, two (p-hydroxybenzene) methane, anthracene dioctyl phthalate, 4,
4 '-diphenyl ether dioctyl phthalate, 5-sulfo group sodium M-phthalic acid, the 5-tetrabutylThe dicarboxylic acids such as M-phthalic acid, glycolic, hydroxyl
The hydroxy carboxylic acid such as base propanoic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxy benzoic acid, caprolactone, valerolactone, propiolactone,
The lactone such as undecalactone, 1,5-oxepane-2-ketone.As for the copolymerization amount of other monomeric unit as described above,
Relative to monomeric unit entirety 100mol% in the polymer of polylactic acid based resin, preferably 0～30mol%, more preferably 0
～10mol%.It addition, in above-mentioned monomeric unit, preferably select the composition with biological degradability according to purposes.
The matter average molecular weight of polylactic acid based resin used in the present invention, from the molecular weight of reacted block copolymer and
From the viewpoint of operability time melted, preferably 5000～1000000, more preferably 10000～500000, most preferably
It is 100000～300000.It addition, the matter average molecular weight in the present invention refers to, different at hexafluoro with gel permeation chromatography (GPC)
The good solvents such as propanol are measured, the molecular weight calculated by polymethyl methacrylate scaling method.
As the method manufacturing polylactic acid based resin used in the present invention, can be by by direct with other raw material for lactic acid
The method of dehydrating condensation or the method making lactide and other cyclic ester intermediate carry out ring-opening polymerisation obtain.Such as, directly
Connect dehydrating condensation and in the case of manufacturing, make lactic acid class or lactic acid class and hydroxycarboxylic acid preferably at organic solvent, particularly benzene
Carry out azeotropic dehydration condensation in the presence of ether series solvent, the particularly preferred solvent by distillating from azeotropic removes water and makes essence
On become anhydrous state the method for solvent Returning reacting system be polymerized, thus obtain the polymer of high molecular.
It addition, it is known that by using the catalyst such as tin octoate to make the cyclic ester intermediate such as lactide under reduced pressure open
Cyclopolymerization can also obtain the polymer of high molecular.Now, by using water when being heated to reflux in regulation organic solvent
Divide and the method for removing condition of low molecular compound, polyreaction make catalysqt deactivation to suppress the side of depolymerization reaction after terminating
Method, manufactured polymer is carried out heat-treating methods etc., it is possible to obtain the polymer that lactide amount is few.
The resin (resin (A)) of at least one hydroxyl (intramolecular have)
In the present invention, use resin (A) as the manufacture raw material of block copolymer.In the present invention, relative to poly-breast
Acid is the ester bond between the lactic acid units-lactic acid units in resin, is that starting point carries out ester exchange reaction, institute with the hydroxyl of resin (A)
It is that to have the resin of at least one hydroxyl be important to intramolecular with resin (A).But, resin (A) be polylactic acid based resin with
Outer, intramolecular has the resin of at least one hydroxyl.It addition, for resin (A), according to purposes, preferably select and there is biology
The resin of degradability.
As resin (A), contain the resin of hydroxyl as molecular end, can enumerate, gathering beyond polylactic acid based resin
Ester system resin, polyethers system resin, polyacetals system resin etc..It addition, contain the resin of hydroxyl as side chain, can enumerate, poly-second
Enol system resin, ethylene-vinyl alcohol copolymer resin, polysaccharide, the carboxylate of polysaccharide, the etherate of polysaccharide, polysaccharide
Deoxidation halogenide, the oxide of polysaccharide, hydroxyl modification polyolefin-based resins etc..Soft in order to give polylactic acid based resin
Property, the glass transition temperature of resin (A) is preferably-70～50 DEG C, more preferably-70～40 DEG C.
In the middle of them, high and polylactic acid based resin the intermiscibility of the effect from the flexibility improving polylactic acid based resin is high
Aspect set out, as resin (A), preferably the polyester based resin beyond polylactic acid based resin and/or polyethers system resin, more excellent
Elect polyethers system resin, more preferably poly alkylene glycol resin as.
As the poly alkylene glycol resin of resin (A), particularly preferably Polyethylene Glycol, polypropylene glycol, poly-four methylenes
Base glycol, polyethylene glycol propylene glycol copolymers, the most most preferably Polyethylene Glycol.Polyethylene Glycol, due to soft and and polylactic acid
The affinity being resin is high, so the block copolymer of polylactic acid based resin and Polyethylene Glycol is in its flexibility, poly lactic acid series tree
The plasticizing efficiency aspect of fat is excellent.
As for the matter average molecular weight of resin used in the present invention (A), from the molecular weight of reacted block copolymer and
Flexibility and melted time operability from the viewpoint of, preferably 1000～1000000, more preferably 5000～500000,
More preferably 5000～100000, most preferably 5000～30000.
(ester exchange catalyst)
For the present invention, it is important for making polylactic acid based resin, resin (A) and ester exchange catalyst melt at normal pressure.
I.e., in the present invention, carried out the manufacture of block copolymer by ester-interchange method, now use ester exchange catalyst to become weight
Want.
As the ester exchange catalyst in the present invention, although be not particularly limited, but can enumerate, such as metal, gold
Belong to salt, sulfur acid, nitrogen-containing basic compound.
As the example of metal, can enumerate, manganese, magnesium, titanium, zinc, ferrum, aluminum, cerium, calcium, barium, cobalt, lithium, sodium, potassium, caesium, lead,
Strontium, stannum, antimony, germanium, yttrium, lanthanum, indium, zirconium etc..
As slaine, can enumerate, the acylate of metal, the nitrate of metal, the phosphate of metal, the boron of metal
Hydrochlorate, the halide salts of metal, the hydroxide salt etc. of metal.It addition, as the metal used in slaine, can enumerate
With the metal as the example of above-mentioned metal.As the example of organic acid, can enumerate, carboxylic acid, sulfur acid, carbonic acid, phenol etc..
As vitriolated example, can enumerate, sulphuric acid, sulfoacid compound, sulfinic acid compound, sulfenic acids compound.
As nitrogen-containing basic compound, can enumerate, quaternary ammonium salt, tertiary amines, secondary amine class, primary amine class, pyridines, imidazoles
Class, ammonia etc..
Wherein, the degree from the reduction of the dispersibility resin, the decomposition of resin and molecular weight, the effect as catalyst
From the viewpoint of, the ester exchange catalyst in the present invention is preferably slaine, more preferably metal acylate and/or
The halide salts of metal.Particularly, from selecting the little ester exchange catalyst of the corrosivity of polymeric kettle and extruder, unit mass
The high ester exchange catalyst of ester exchange catalytic capability and be difficult to occur the viewpoint of the ester exchange catalyst oozed out from resin to go out
Send out, as acylate and/or the halide salts of metal of metal, it is however preferred to have having of the alkyl of carbon number 0～10
Machine acid and the salt (acylate of metal) of metal and/or the halide salts of metal.It addition, in the present invention, carbon number is
The alkyl of 0 refers to, intramolecular does not have the meaning of alkyl.
Additionally, the block copolymer obtained for the present invention, if it is considered that at the purposes of agriculture and forestry, refuse bag, heap
Fertile bag etc. needs the probability used in the purposes of biological degradability, and ester exchange catalyst the most used in the present invention is the most right
The catalyst that biological safety is high.Select as the ability of ester exchange catalyst if taken into account thereon, then ester exchange
Catalyst is preferably the acylate of metal and/or the halide salts of metal, as particularly preferred ester exchange catalyst, permissible
Enumerate, the organic acid of alkyl with carbon number 0～10 as follows and the salt (acylate of metal) of metal or
The halide salts of metal as follows.
Particularly preferred as the acylate of metal, there is organic acid and the metal of the alkyl of carbon number 0～10
The concrete example of salt, the most do not have the carbon number 1 of hydroxyl～the carboxylic acid of 10 with selected from magnesium, titanium, stannum, zinc, ferrum, aluminum,
The salt that metal in calcium, potassium is formed.It addition, the concrete example of the halide salts of particularly preferred metal, for example, selected from magnesium, titanium,
The halogenide of the metal in stannum, zinc, ferrum, aluminum, calcium, potassium.
It addition, in the present invention, it is also possible to and with two or more different ester exchange catalyst.
(manufacture method of the block copolymer of polylactic acid based resin and resin (A))
The manufacture method of the block copolymer of the present invention is characterised by, supplies the poly lactic acid series as raw material to reactor
Resin, resin (A) and ester exchange catalyst, carry out melting (experience normal pressure melts operation) at ambient pressure.
By the present invention in that polylactic acid based resin and resin (A) carry out ester exchange reaction to manufacture block copolymer.And,
Ester exchange reaction designated herein refers to, makes some ester bond have an effect with hydroxyl, carboxylic acid group or other ester bond, and in ester bond
Hydroxyl or carboxylic acid group exchange, generate the reaction with the initial different types of ester bond of ester bond.Particularly, in the present invention
In, main purpose is that the ester bond of the hydroxyl Yu polylactic acid based resin by making resin (A) is had an effect at polylactic acid based resin
And introduce ester bond between resin (A).
Melt the melt temperature in operation as normal pressure, although according to the kind of reactor, the fusing point of polylactic acid based resin,
The fusing point of resin (A), the viscosity of polylactic acid based resin and the viscosity of resin (A) and different, but, particularly when
In view of fusing point and the heat decomposition temperature of polylactic acid based resin, then the temperature during normal pressure melts operation is preferably 150～250 DEG C,
More preferably 180～240 DEG C.It addition, the polylactic acid based resin used and resin (A), hydrolysis during in order to prevent melted and
Coloring, carries out fully being dried making moisture rate reduce the most in advance.The water quantities of polylactic acid based resin and resin (A) is the most altogether
1200ppm (quality criteria) below, more preferably 500ppm (quality criteria) below, more preferably 200ppm (quality base
Accurate) below.
The addition mass ratio of polylactic acid based resin and resin (A) is not particularly limited, it is preferable that scope is with quality
Ratio is calculated as 95:5～5:95.Particularly, the master that the block copolymer of product is used for as the resin of flexibility molded body
In the case of composition, the addition mass ratio of polylactic acid based resin and resin (A) is preferably 95:5～50:50, more preferably
90:10～60:40.It addition, in the case of using block copolymer as the plasticizer of polylactic acid based resin, poly lactic acid series tree
The addition mass ratio of fat and resin (A) is preferably 80:20～5:95, more preferably 75:25～10:90, and more preferably 70:
30～30:70.
Addition as ester exchange catalyst, although according to the kind of reactor, reaction temperature, response time, reaction
Atmosphere etc. and different, but, relative to total 100 mass parts of polylactic acid based resin and resin (A), preferably 0.001
～5 scopes of mass parts, the more preferably scope of 0.005～1 mass parts.As long as the addition of ester exchange catalyst is relative
The scope that total 100 mass parts is 0.001～5 mass parts in polylactic acid based resin and resin (A), it is possible to by obtained
The coloring of block copolymer, molecular weight reduce and the generation of lactide is limited in Min..
In the present invention, during in order to suppress ester exchange reaction, produce lactide, carry out normal pressure at ambient pressure and melt operation be
Important.Normal pressure in the present invention refers to, normal pressure melts the air pressure in operation 5 × 104～1.5 × 105In the range of Pa, excellent
Elect 7 × 10 as4～1.3 × 105Pa, more preferably 9 × 104～1.1 × 105Pa.It addition, melt in operation at this normal pressure,
In order to suppress hydrolysis and the oxidation Decomposition of resin, preferably make reactor under non-active gas atmosphere.
Normal pressure melts the reactor used in operation and is not particularly limited, such as batch reactor, and Ke Yiju
Go out, the test tube of band agitating device, longitudinal type or horizontal type tank reactor or kneading machine etc..As flow reactor, can enumerate,
Single screw extrusion machine, double screw extruder, other multi-screw extruder.Multi-screw extruders more than two screw rods, its screw rod revolves
Turning direction can be equidirectional, it is also possible to be different directions.
Wherein, from the viewpoint of shortening response time and operability, normal pressure melts the reactor of operation and is preferably continuously
Formula reactor, more preferably double screw extruder.That is, normal pressure melts operation, preferably in flow reactor, particularly
Carry out in double screw extruder.In double screw extruder, melted the rapidest due to polylactic acid based resin and resin (A)
Ground is carried out, and resin distributive mixing each other and dispersion mixing are carried out expeditiously, thus the ester bond of polylactic acid based resin with
The collision probability of the hydroxyl of resin (A) increases, and its result, their ester exchange reaction was carried out with the short time.
As previously mentioned, although normal pressure melts operation preferably to be carried out in double screw extruder, but as such pair of spiral shell
The screw rod of bar extruder is constituted, and in order to ensure the resin time of staying required for reaction and mixing power, reverse pinch is preferably used
Conjunction dish, screw diameter is preferably 10～400mm, and L/D is preferably 20～200.
In the case of reactor is double screw extruder, air pressure is measured by steam vent.
The time required for operation is melted as normal pressure, in the case of using the batch reactor that mixing property is low, excellent
Elect 30 minutes～5 hours as.In contrast, in the case of the flow reactor with double screw extruder as representative, normal pressure
The time of melted operation is equivalent to the time of staying of the resin in reactor, and it is preferably 5～30 minutes, and more preferably 5
～15 minutes.
The block copolymer obtained by the manufacture method of the present invention, by making the ester exchange catalyst of residual inactivate, can
To improve its storage stability further.As the deactivator used with such purpose, can enumerate, such as aminoacid, phenol
Class, hydroxy carboxylic acid, diones, amine, oxime, phenanthroline class, pyridine compounds, dithio compound, diazonium compound, mercaptan
Class, porphyrin, containing nitrogen as the phenols of coordination atom, carboxylic acid, phosphoric acid, phosphate ester, phosphate metal salt, phosphorous acid, phosphorous acid
The phosphorus compounds such as ester, phosphorous acid slaine.It addition, these deactivators are possible not only to be used alone, but also also mix together.From poly-
The aspect of the hydrolytic resistance of lactic acid series resin is set out, more preferably phosphorus compound, further preferred purity 98 matter in these deactivators
The phosphoric acid crystallization of amount more than % or phosphorous acid crystallization.
As the method adding deactivator, in the case of batch reactor, have after ester exchange reaction terminates temporary transient
Make reactor stop and adding deactivator, the most again making the method that reactor runs.With double screw extruder as representative
In the case of flow reactor, there is the method that the side feeder from extruder adds deactivator.
As for the addition of deactivator, relative to ester exchange catalyst 1 mass parts added in manufacturing process, it is preferably
0.01～10 mass parts, more preferably 0.1～5 mass parts.
For the matter average molecular weight of the block copolymer that the present invention is obtained, using by this block copolymer as molded body
Main constituent for the purpose of in the case of, in order to meet practicality mechanical property, its matter average molecular weight be preferably 10000～
1000000, more preferably 50000～500000.It addition, utilizing this block copolymer situation as additives such as plasticizers
Under, in order to show softnessization and resistance to exudative, its matter average molecular weight be preferably 1000～500000, more preferably 5000～
100000, more preferably 5000～50000.
(block copolymer and the mixture of polylactic acid based resin)
The block copolymer that the present invention is obtained can be with polylactic acid based resin using.In this case, block copolymerization
Thing can also be as the plasticizer function of polylactic acid based resin.Like this, at the block copolymer that the present invention is obtained
In the case of using as the plasticizer of polylactic acid based resin, in order to make block copolymer be dispersed in polylactic acid based resin,
Polylactic acid based resin and block copolymer can be carried out melting mixing, it is possible to so that polylactic acid based resin and block copolymer are molten
Solution, in the good solvents such as chloroform, makes solvent volatilization or makes resin separate out in poor solvent.
In the case of block copolymer is used as the plasticizer of polylactic acid based resin, for polylactic acid based resin
With the content ratio of block copolymer, in total 100 mass % of block copolymer and polylactic acid based resin, preferably comprise 3
～70 block copolymers of mass %, more preferably contain 5～60 mass %, further preferably containing 5～50 mass %.If it is embedding
The content ratio of section copolymer is in above-mentioned scope, it is possible to improve the flexibility of polylactic acid based resin and resistance to impact, suppression embedding
Oozing out of section copolymer.
In the case of block copolymer is used as polylactic acid based resin plasticizer, except polylactic acid based resin
Beyond block copolymer, resin combination can also mix other thermoplastic resin, general particle, additive.
The normal pressure manufacturing block copolymer melts operation, as it was previously stated, preferably (following, by this pair at double screw extruder
Screw extruder is referred to as double screw extruder 1) in carry out.Additionally, using block copolymer as the plasticising of polylactic acid based resin
Agent and use etc., manufacture the mixture of polylactic acid based resin and block copolymer in the case of, the poly lactic acid series tree being preferably as follows
The manufacture method of the mixture of fat and block copolymer, it is characterised in that the block copolymerization that will manufacture in double screw extruder 1
Thing is importing directly into other double screw extruder in double screw extruder 1 and (below, is claimed by the double screw extruder that this is other
For double screw extruder 2) in, mix with polylactic acid based resin in this double screw extruder 2.That is, polylactic acid is being manufactured
When being the mixture of resin and block copolymer, polymer pipe etc. is preferably used the block manufactured with double screw extruder 1 is total to
Polymers is introduced directly into the stage casing of double screw extruder 2 with molten condition by methods such as side chargings, in double screw extruder 2 with
Polylactic acid based resin mixes.Here, directly it is meant that, block copolymer is being imported in double screw extruder 1
Time in double screw extruder 2, this block polymer in the case of keeping more than glass transition temperature from twin-screw extrusion
Import in machine 1 in double screw extruder 2.Such as, block copolymer is being discharged in double screw extruder 1, with this block
Copolymer become such in the state of below glass transition temperature imports to double screw extruder 2 in the case of, it is impossible to understand
For designated herein direct.It addition, in the case of block copolymer has multiple glass transition temperature, block copolymerization will be made
Thing imports to double screw extruder 2 in the case of being maintained at more than the highest glass transition temperature in double screw extruder 1
Interior the most direct.
In the case of manufacturing the block copolymer mixture with polylactic acid based resin, the matter that there is block copolymer is divided equally
Son amount is little, the situation that additionally glass transition temperature is low, and such block copolymer exists the probability being difficult to sheet stock.At this
In the case of Zhong, need temporarily to cool and solidify the block copolymer obtained, then carry out pulverization process.If in contrast,
Use and the block copolymer using double screw extruder 1 to obtain is introduced directly into double screw extruder 2 and at double screw extruder 2
In carry out the technique that mixes with polylactic acid based resin, then can omit above-mentioned cooling, the time and labor of pulverizing, so excellent
Choosing.
Screw rod composition, screw diameter, L/D and the time of staying of double screw extruder 1 and double screw extruder 2, preferably
With the preferred screw rod composition of aforesaid double screw extruder, screw diameter, L/D and as the time of staying.It addition, twin screw
Extruder 1 and double screw extruder 2 can also be compositions of the same race.
It addition, carry out the double screw extruder 1 of the manufacture of block copolymer, due to aforesaid reason, need for normal pressure.Often
The scope of pressure is identical with aforementioned range.On the other hand, in the method, double screw extruder 2 due to and do not contribute to block altogether
The generation of polymers, so in double screw extruder 2, air pressure is it is not necessary to be normal pressure, it is also possible to it is set under Jian Ya.
It addition, as the method manufacturing polylactic acid based resin and the mixture of block copolymer, there is also following poly-breast
Acid is the manufacture method of resin and the mixture of block copolymer, it is characterised in that with respect to double screw extruder manufacture
Block copolymer, put into polylactic acid based resin from the side feeder of the same double screw extruder manufacturing this block copolymer,
Thus in the same double screw extruder manufacturing this block copolymer, this block copolymer and polylactic acid based resin are mixed
Close.In the method, in addition to can omitting the time and labor of the cooling of block copolymer, pulverizing as described above,
The double screw extruder needed is only 1, can be constituted by device and simplify, so preferably.
As the preferred screw rod composition of the double screw extruder that this method is used, can enumerate, gather breast with putting into
Acid is that forward side addition kneading disk compared by the side feeder of resin.It addition, for screw diameter, L/D and the time of staying, preferably with
Preferred screw diameter, L/D and the time of staying of aforesaid double screw extruder are same.It addition, for extrusion temperature, preferably will
Temperature near this kneading disk is set to 200～280 DEG C, and catalytic amount is preferably 0.05～5 mass parts.This is because, we
The manufacture being substantially carried out block copolymer in method is that the position of main feed device from double screw extruder is to adding poly lactic acid series
The position of the side feeder of resin, is the most only a part for double screw extruder, needs to carry out the most efficiently instead
Should.It addition, when adding polylactic acid based resin from side feeder, add deactivator the most simultaneously.
In the method, it is the main feed device from double screw extruder due to be substantially carried out the manufacture of block copolymer
Position, to the position of the side feeder adding polylactic acid based resin, in this position, due to above-mentioned reason, needs to carry out at ambient pressure
Reaction.The scope of normal pressure is identical with aforesaid scope.On the other hand, for, after the position of side feeder, the most not having
Help the generation of block copolymer.Therefore, in this interval, air pressure is it is not necessary to be normal pressure, it is also possible to it is set under Jian Ya.
It addition, the polylactic acid based resin used in the mixture of polylactic acid based resin and block copolymer, it is possible to use
The resin identical with the polylactic acid based resin hereinbefore illustrated as the raw material of block copolymer.
In the compositions of the block copolymer obtained containing the present invention, known antioxygen can also be used as required
Agent, crystallization nucleating agent, ultra-violet stabilizer, stainblocker, delustering agent, deodorizer, fire retardant, weather resisting agent, antistatic additive, from
The additives such as sub-exchanger, viscosifier, defoamer, coloring pigment, dyestuff, lubricant, foaming agent, other resin.For these
The addition of additive, as long as not damaging the scope of the effect that the present invention is realized, is just not particularly limited, but relative to containing
Having compositions 100 mass % of block copolymer, additive is preferably 0.01～30 mass %, more preferably 0.01～20 matter
Amount %, more preferably 0.01～10 mass %.
The block copolymer that the present invention is obtained, from the viewpoint of foul smell and hydrolytic resistance, its residual lactide amount is excellent
Elect below 1.00 mass % as, below more preferably 0.70 mass %, more preferably below 0.50% mass.
It addition, the block copolymer that the present invention is obtained, due to preferably as the polylactic acid based resin of raw material and resin (A)
Do not remain, it is advantageous to its GPC elution curve only exists one be derived from high molecular peak (unimodality).It addition, at polylactic acid
In the case of being resin and resin (A) residual, its GPC elution curve exists 2 and is derived from high molecular peak (bimodality) or deposits
More than 2.
It addition, the block copolymer that the present invention is obtained, the resin (A) preferably as raw material does not remains.Therefore, for
Lower defined TmA0 and TmA, preferably TmA0-TmA are more than 7.0 DEG C, more preferably more than 9.0 DEG C.
TmA0: the melting peak temperature being derived from resin (A) read from the figure of the DSC temperature-rise period of resin (A) monomer.
TmA: the melting peak temperature being derived from resin (A) segment read from the figure of the DSC temperature-rise period of block copolymer.
It addition, in the situation of the block copolymer that the present invention is obtained Yu the mixture flaking of polylactic acid based resin
Under, for the sheet obtained, in order to show sufficient flexibility, its tensile modulus of elasticity is preferably 100～1000MPa.Stretching
Elastic modelling quantity is more preferably 100～950MPa, and more preferably 100～900MPa.
It addition, above-mentioned containing block copolymer with the sheet of polylactic acid based resin, need block copolymer not from poly lactic acid series
Resin departs from, and i.e. needs it resistance to exudative.As resistance to exudative index, the hot water extraction rate of sheet is preferably in following ranges.That is,
Sheet has been carried out by the distilled water seethed with excitement at 1 atmosphere pressure 1 hour process time rate of mass reduction be preferably 5.0% with
Under, more preferably less than 3.0%.Embodiment
Embodiment is illustrated below the present invention is specifically described, but the present invention is not by any limit of these embodiments
System.
[measuring and evaluation methodology]
Mensuration shown in embodiment, evaluation are carried out under conditions of as described below.
(1) elastic modelling quantity (MPa)
The TENSILON UCT-100 using (strain) オ リ エ Application テ ッ Network to produce carries out stress-strain measurement, use stress-
The initial straight line portion of strain curve, by the stress difference between 2 on straight line divided by the strain differential between identical 2, thus counts
Calculate tensile modulus of elasticity.Specifically, compressed tablet determine long 150mm, the rectangle sample of wide 10mm, press from both sides at incipient extension
Tool spacing 50mm, draw speed were surveyed according to the method for regulation in JIS K 7127 (1999) under conditions of 200mm/ minute
Fixed.It addition, mensuration carried out 5 times, calculate its meansigma methods.
(2) lactide amount
By the sample dissolution of generation in dichloromethane, concentration is regulated to 1g/20ml, then adds acetone 60ml, and then
Carry out ultrasonic agitation while the hexamethylene 320ml that drips, so that component of polymer separates out.By centrifugation and aperture
Precipitate is removed by the PTFE filter of 0.45 μm, is fabricated to sample liquid.Use gas chromatogram GC-17A (society of Shimadzu Seisakusho Ltd.
System) at post: DB-17MS type (J&W society system), column temperature: 80～250 DEG C, 10 DEG C/min, carrier gas: to this sample liquid under conditions of He
It is analyzed.It addition, use the sample liquid of the lactide monomer changing concentration to make standard curve in advance, utilize this standard bent
The lactide amount (quality %) of test portion tried to achieve by line.
(3) hot water extraction rate
As resistance to exudative index, measure hot water extraction rate.For in advance at temperature 23 DEG C, the environment of humidity 65%RH
The middle damping compressed tablet of more than 1 day, measures quality before treatment.Then, in the distilled water seethed with excitement at 1 atmosphere pressure right
Sheet carries out 1 hour impregnation process, again carries out damping, the quality after then mensuration processes under conditions of as before process.
Then, hot water extraction rate is calculated by following formula.
Hot water extraction rate (quality %)=(quality after quality-process before treatment) × 100/ quality before treatment
(4)GPC
For matter average molecular weight, it is measured by gel permeation chromatography (GPC), is changed by polymethyl methacrylate
Algorithm calculates.It addition, the calculating of matter average molecular weight, only in the elution curve of the sample obtained, only exist one and be derived from
Carry out in the case of high molecular peak (unimodality), not there are two macromolecules being derived from polylactic acid based resin and resin (A)
Peak (bimodality) in the case of, or have be derived from plural high molecular peak in the case of carry out.The mensuration of GPC makes
2695 types produced with Waters company are carried out, and detector uses differential refractometer 2414 type of WATERS company, and pump uses
The MODEL510 of WATERS company, post uses and is carried out by the post that 2 Shodex HFIP-806M are connected in series.As for measuring bar
Part, flow velocity is set to 0.5mL/ minute, column temperature be set to 40 DEG C, use add 5mM sodium trifluoroacetate hexafluoroisopropanol as molten
Agent, injects the solution of 0.2mL test portion concentration 0.1 mass %.
(5)DSC
Use the differential scanning calorimeter RDC220 that セ イ U イ Application ス Star Le (strain) produces, the sample 5mg that will generate
It is contained in aluminum dish, is warming up to 220 DEG C from 25 DEG C with the programming rate of 20 DEG C/min, keep 5 minutes melting, so at 220 DEG C
Rear quenching is to 25 DEG C.Then, from the figure of this temperature-rise period, reading is derived from melting peak temperature TmA (DEG C) of resin (A) segment.Separately
Outward, using unreacted resin (A) as sample, the melting peak temperature TmA0 of resin (A) is tried to achieve by method similar to the above
(DEG C), calculates TmA0-TmA.
[polylactic acid based resin]
(4032D)
Poly (l-lactic acid), " 4032D " that Natureworks produces, matter average molecular weight 200000, D body burden 1.4mol%, molten
Point 166 DEG C.Use the resin being under reduced pressure dried 5 hours in advance in vacuum drying oven at 100 DEG C.
(4060D)
Poly (l-lactic acid), " 4060D " that Natureworks produces, matter average molecular weight 200000, D body burden 12.0mol%,
Without fusing point.Use the resin being under reduced pressure dried 7 hours in advance in vacuum drying oven at 50 DEG C.
It addition, matter average molecular weight uses the Waters2695 that Japan ウ ォ タ ズ (strain) produces, with polymethyl
Acid methyl ester uses hexafluoroisopropanol solvent to be measured as standard at column temperature 40 DEG C.
[resin (A)]
(PEG6000S)
Polyethylene Glycol, " PEG6000S " that chemical conversion industrial group of Sanyo produces, matter average molecular weight 8000, TmA0 is 64.0
℃.Use the resin being under reduced pressure dried 7 hours in advance in vacuum drying oven at 30 DEG C.
(Ecoflex)
Polytetramethylene glycol adipate ester-terephthalate, " the Ecoflex F Blend C1200 " that BASF produces, matter is equal
Molecular weight 60000, TmA0 is 120.2 DEG C.Use the tree being under reduced pressure dried 7 hours in advance in vacuum drying oven at 80 DEG C
Fat.
[ester exchange catalyst]
(acetic acid Mg)
As slaine (acylate of metal), use magnesium acetate 4 hydrate (producing with Wako Pure Chemical Industries).
(chlorination Mg)
As slaine (halide salts of metal), use magnesium chloride hexahydrate (producing with Wako Pure Chemical Industries).
(octanoic acid Sn)
As slaine (acylate of metal), use 2 ethyl hexanoic acid stannum (II) (producing with Wako Pure Chemical Industries).
(p-TSA)
As sulfur acid, use p-methyl benzenesulfonic acid (producing with Wako Pure Chemical Industries).
(embodiment 1)
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, join band agitating device
In test tube, at air pressure 1.0 × 105The blanket of nitrogen of Pa stirs while at 200 DEG C melted 4 hours, cool down, solidify thus
Obtain Sample A.The Sample A obtained carries out lactide amount, matter average molecular weight and DSC measure.
And then, weigh 30 mass parts Sample A, 20 mass parts 4032D, 50 mass parts 4060D, join band agitating device
In test tube, at air pressure 1.0 × 105The blanket of nitrogen of Pa stirring while melting 1 hour at 240 DEG C, cooling down, solidifying, from
And obtain sample B.The sample B obtained is pulverized, is then under reduced pressure dried 7 hours at 50 DEG C in vacuum drying oven,
Pressurize at 220 DEG C, thus obtain the isotropism compressed tablet of thickness 200 μm.Measure the elastic modelling quantity of compressed tablet obtained and
Hot water extraction rate.
It addition, for embodiment 2 and comparative example 1, except and melting the composition of the raw material of input test tube according to Tables 1 and 2
Melt beyond temperature changes, in the way of similarly to Example 1, obtain sample.
Additionally, for comparative example 2～3, put into composition and the melt temperature of the raw material of test tube according to table 2 change, obtaining
Vacuum pump is used to make invisible spectro air pressure become 1.0 × 10 during Sample A3Pa, in addition obtains in the way of similarly to Example 1
Obtain sample.
(embodiment 3)
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, be blended, put into day
In the double screw extruder TEX30 α (L/D=35, screw diameter=30mm) that this system steel is produced, with screw speed 200rpm,
Inlet amount 10kg/h carries out melting, mixing, discharge from mouth die, cool down, solidify, thus obtain Sample A.It addition, for TEX30 α
Temperature set, before hopper bottom to the first kneading part (from screw front end measure L/D=25 position) be set as 80 DEG C,
It is set as 200 DEG C by after the first kneading part.Set it addition, will be located in the steam vent from the position that screw front end measures L/D=20
For open state.The air pressure of this position is 1.0 × 105Pa.The Sample A obtained is carried out lactide amount, matter average molecular weight and
DSC measures.
Additionally, weigh 30 mass parts Sample A, 20 mass parts 4032D, 50 mass parts 4060D, join band agitating device
In test tube, at air pressure 1.0 × 105The blanket of nitrogen of Pa stirring while melting 1 hour at 240 DEG C, cooling down, solidifying, from
And obtain sample B.The sample B obtained is pulverized, is then under reduced pressure dried 7 hours at 50 DEG C in vacuum drying oven,
Pressurize at 220 DEG C, thus obtain the isotropism compressed tablet of thickness 200 μm.Measure the elastic modelling quantity of compressed tablet obtained and
Hot water extraction rate.
It addition, for embodiment 4～10, comparative example 4～7, except putting into the raw material of TEX30 α according to Tables 1 and 2 change
Composition and extrusion temperature beyond, in the way of similarly to Example 3, obtain sample.
Additionally, for comparative example 8, put into composition and the extrusion temperature of the raw material of TEX30 α according to table 2 change, and will
The steam vent from the position that screw front end measures L/D=20 that is positioned at of TEX30 α is connected with vacuum pump, makes the air pressure of this position become
It is 3.0 × 103Pa, in addition obtains sample in the way of similarly to Example 3.
The physical property of the sample obtained is shown in Tables 1 and 2.
(embodiment 11)
As double screw extruder 1, use the TEX30 α (L/D=35, screw diameter=30mm) that JSW produces,
As double screw extruder 2, use the TEX44 α (L/D=38, screw diameter=44mm) that JSW produces, with will be from double
The stage casing (measuring the position of L/D=18 from screw front end) that the resin side that screw extruder 1 is discharged feeds to double screw extruder 2
Mode constituent apparatus.
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, be blended, put into double
In screw extruder 1, carry out melting with screw speed 200rpm, inlet amount 10kg/h, mixing.It addition, for twin-screw extrusion
The temperature of machine 1 sets, and is set as (measuring the position of L/D=25 from screw front end) before hopper bottom to the first kneading part
80 DEG C, it is set as 200 DEG C by after the first kneading part.It addition, make being positioned at of double screw extruder 1 measure L/D from screw front end
The steam vent of the position of=20 is open state.The air pressure of this position is 1.0 × 105Pa。
Additionally, weigh 67 mass parts 4032D, 167 mass parts 4060D, it is blended, puts in double screw extruder 2,
Carry out melting with screw speed 200rpm, inlet amount 23.3kg/h, mixing.It addition, the temperature for double screw extruder 2 sets
Fixed, before hopper bottom to the first kneading part, (position of L/D=28 will be measured from screw front end) and be set as 150 DEG C, by the
220 DEG C it are set as after one kneading part.It addition, make double screw extruder 2 be positioned at from screw front end measure L/D=20 position
Steam vent be open state.The air pressure of this position is 1.0 × 105Pa.The resin will discharged from the mouth die of double screw extruder 2
Cooling, solidification, thus obtain sample C.The sample C obtained is pulverized, then in vacuum drying oven under reduced pressure at 50 DEG C
It is dried 7 hours, pressurizes at 220 DEG C, thus obtain the isotropism compressed tablet of thickness 200 μm.Measure the compressed tablet obtained
Elastic modelling quantity and hot water extraction rate.
It addition, for embodiment 12 and comparative example 9, except putting into the raw material of double screw extruder 1 and 2 according to table 3 change
Composition beyond, in the way of similarly to Example 11, obtain sample.
The physical property of the sample obtained is illustrated in table 3.
Table 3
(embodiment 13)
As double screw extruder, use the TEX30 α (L/D=35, screw diameter=30mm) that JSW produces,
In the stage casing (measuring the position of L/D=18 from screw front end) of double screw extruder, side feeder is set.
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, be blended, put into double
The main hopper of screw extruder, carries out melting with screw speed 200rpm, inlet amount 10kg/h, mixing.It addition, for twin screw
The temperature of extruder 1 sets, and sets (measuring the position of L/D=25 from screw front end) before hopper bottom to the first kneading part
It is set to 80 DEG C, 240 DEG C will be set as from the first kneading part to side feeder.It addition, make being positioned at from screw rod of double screw extruder 1
The steam vent of the position that L/D=20 is measured in front end is open state.The air pressure of this position is 1.0 × 105Pa。
Additionally, weigh 67 mass parts 4032D, 167 mass parts 4060D, it is blended, puts in the feeder of side, carry out
Melted, mixing.Temperature later for side feeder is set as 200 DEG C.It addition, the tree will discharged from the mouth die of double screw extruder
Fat cooling, solidification, thus obtain sample D.The sample D obtained is pulverized, then under reduced pressure at 50 DEG C in vacuum drying oven
Under be dried 7 hours, pressurize at 220 DEG C, thus obtain the isotropism compressed tablet of thickness 200 μm.Measure the compacting obtained
The elastic modelling quantity of sheet and hot water extraction rate.
It addition, for embodiment 14～15 and comparative example 10～11, except putting into double screw extruder according to table 4 change
Beyond the composition of raw material, in the way of similarly to Example 13, obtain sample.
The physical property of the sample obtained is illustrated in table 4.
(embodiment 16)
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, be blended, put into プ
In the single screw extrusion machine GT-40 (L/D=28, screw diameter=40mm) that ラ ス チ ッ Network engineering institute produces, turn with screw rod
Speed 50rpm, inlet amount 10kg/h carry out melting, mixing, discharge from mouth die, cool down, solidify, thus obtain Sample A.It addition, it is right
Temperature in GT-40 sets, and hopper bottom is set as 80 DEG C, will be set as 200 DEG C later.It addition, make the steam vent in stage casing
For open state.The air pressure of this position is 1.0 × 105Pa.The Sample A obtained is carried out lactide amount, matter average molecular weight and
DSC measures.
Additionally, weigh 30 mass parts Sample A, 20 mass parts 4032D, 50 mass parts 4060D, join band agitating device
In test tube, at air pressure 1.0 × 105The blanket of nitrogen of Pa stirring while melting 1 hour at 240 DEG C, cooling down, solidifying, from
And obtain sample B.The sample B obtained is pulverized, is then under reduced pressure dried 7 hours at 50 DEG C in vacuum drying oven,
Pressurize at 220 DEG C, thus obtain the isotropism compressed tablet of thickness 200 μm.Measure the springform of the compressed tablet obtained
Amount and hot water extraction rate.
It addition, for comparative example 12, in addition to the composition of the raw material putting into GT-40 according to table 5 change, with embodiment
16 same modes obtain sample.
Additionally, for comparative example 13, the steam vent of GT-40 is connected with vacuum pump, make the air pressure of this position be 3.0 ×
103Pa, in addition, obtains sample in the way of similarly to Example 16.
The physical property of the sample obtained is illustrated in table 5.
Table 5
Industrial applicability
By using the normal pressure as feature of present invention to melt operation, it is possible to obtain the block copolymerization that residual lactide is few
Thing.The block copolymer that the present invention is obtained, by being used alone and mixing with polylactic acid based resin, except can be as soft
Soft resin and beyond using in the molded bodys such as film, it is also possible to as polylactic acid based resin, there is resistance to oozing out suitably
Plasticizer and use.
Claims (5)
1. a manufacture method for block copolymer, described block copolymer is that the block of polylactic acid based resin and resin (A) is total to
Polymers, it is characterised in that polylactic acid based resin, resin (A) and ester exchange catalyst are carried out normal pressure in double screw extruder
Melted operation, described resin (A) is the resin that intramolecular has at least one hydroxyl, and described resin (A) is polyethers system resin,
Described normal pressure melts operation and refers to melt at ambient pressure, and described double screw extruder is double screw extruder 1.
The manufacture method of block copolymer the most according to claim 1, it is characterised in that described resin (A) is polyalkylene
Glycol resin.
The manufacture method of block copolymer the most according to claim 1 and 2, it is characterised in that described ester exchange catalyst
Acylate and/or the halide salts of metal for metal.
4. the manufacture method of the mixture of a polylactic acid based resin and block copolymer, it is characterised in that by claim 1
Described method manufactures block copolymer, is introduced directly into other by manufactured block copolymer in double screw extruder 1
In double screw extruder, mix with polylactic acid based resin.
5. the manufacture method of the mixture of a polylactic acid based resin and block copolymer, it is characterised in that by claim 1
Described method manufactures block copolymer, relative to manufactured block copolymer, from the same a pair of manufacturing this block copolymer
The side feeder of screw extruder puts into polylactic acid based resin, thus is manufacturing the same double screw extruder of this block copolymer
Interior this block copolymer and polylactic acid based resin are mixed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012209177 | 2012-09-24 | ||
| JP2012-209177 | 2012-09-24 | ||
| PCT/JP2013/070753 WO2014045717A1 (en) | 2012-09-24 | 2013-07-31 | Method for producing block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104619745A CN104619745A (en) | 2015-05-13 |
| CN104619745B true CN104619745B (en) | 2016-11-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111253A (en) * | 1994-05-03 | 1995-11-08 | 中国科学院成都有机化学研究所 | Method for copolymerization of internal ester (or lactide) and polyether glycol |
| WO2004000939A1 (en) * | 2002-06-20 | 2003-12-31 | Toray Industries, Inc. | Polylactic acid base polymer composition, molding thereof and film |
| JP2004231773A (en) * | 2003-01-30 | 2004-08-19 | Dainippon Ink & Chem Inc | Method for producing polylactic acid copolymer |
| CN102382424A (en) * | 2010-09-01 | 2012-03-21 | 东丽纤维研究所（中国）有限公司 | Components of mixed resin as well as preparation method and formed product of same |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111253A (en) * | 1994-05-03 | 1995-11-08 | 中国科学院成都有机化学研究所 | Method for copolymerization of internal ester (or lactide) and polyether glycol |
| WO2004000939A1 (en) * | 2002-06-20 | 2003-12-31 | Toray Industries, Inc. | Polylactic acid base polymer composition, molding thereof and film |
| JP2004231773A (en) * | 2003-01-30 | 2004-08-19 | Dainippon Ink & Chem Inc | Method for producing polylactic acid copolymer |
| CN102382424A (en) * | 2010-09-01 | 2012-03-21 | 东丽纤维研究所（中国）有限公司 | Components of mixed resin as well as preparation method and formed product of same |
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