CN1400247A - Biodegradable water soluble polyester compound capable of being stored for long time - Google Patents
Biodegradable water soluble polyester compound capable of being stored for long time Download PDFInfo
- Publication number
- CN1400247A CN1400247A CN02127143A CN02127143A CN1400247A CN 1400247 A CN1400247 A CN 1400247A CN 02127143 A CN02127143 A CN 02127143A CN 02127143 A CN02127143 A CN 02127143A CN 1400247 A CN1400247 A CN 1400247A
- Authority
- CN
- China
- Prior art keywords
- water soluble
- soluble polyester
- polyester compound
- parts
- biodegradable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229920000728 polyester Polymers 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 title claims description 17
- 229920000704 biodegradable plastic Polymers 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- -1 alkali metal salt Chemical class 0.000 claims description 22
- 238000004945 emulsification Methods 0.000 claims description 15
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 238000011176 pooling Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229920000229 biodegradable polyester Polymers 0.000 abstract description 3
- 239000004622 biodegradable polyester Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 238000003860 storage Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 206010018612 Gonorrhoea Diseases 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000007774 longterm Effects 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 description 3
- 235000019800 disodium phosphate Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002563 ionic surfactant Substances 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- NGSFWBMYFKHRBD-UHFFFAOYSA-N sodium;2-hydroxypropanoic acid Chemical compound [Na+].CC(O)C(O)=O NGSFWBMYFKHRBD-UHFFFAOYSA-N 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- MSWZFWKMSRAUBD-GASJEMHNSA-N 2-amino-2-deoxy-D-galactopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@H](O)[C@@H]1O MSWZFWKMSRAUBD-GASJEMHNSA-N 0.000 description 1
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920013701 VORANOL™ Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- MSWZFWKMSRAUBD-QZABAPFNSA-N beta-D-glucosamine Chemical compound N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-QZABAPFNSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
To provide a water-based product of a biodegradable polyester, storable for a long period. This water-based product of the biodegradable polyester is obtained by emulsifying a polyester-based biodegradable plastic in which the carboxylic acid is neutralized by an alkali material, by using an emulsifier.
Description
Technical field
The present invention relates to Biodegradable water soluble polyester compound, particularly storage stability excellent biodegradability water soluble polyester compound.
Background technology
As when discarded, enabling by the biodegradable plastic of microbiological degradation in order environment not to be produced detrimentally affect, ester plastic is used by people always, but general polyester biodegradable plastic is mainly used in injection molding processing purposes, has free carboxy acid's unreacted monomer, oligopolymer and mixture of polymers existence usually as end.
Obtaining the emulsification of this polyester biodegradable plastic for example, the technology majority of resin film and coating is known, for example special opening discloses the emulsion that uses polycarboxylic acid salt's dispersion agent to obtain in the flat 2-227438 communique, the spy opens to disclose in the 2001-11294 communique and uses macromolecule dispersing agent to disperse the material that obtains, and special opening discloses the material that uses the main emulsifying agent that is made of anionic emulsifier to obtain in the flat 10-101911 communique.
But, the emulsion that adopts these prior aries to obtain exist pH low, probably can hydrolysis take place in time, be difficult to the problem of Long-term Storage.
Summary of the invention
The present invention In view of the foregoing proposes, and provides a kind of and suppresses hydrolysis after the water systemization and Biodegradable water soluble polyester compound that can Long-term Storage, and a kind of water system thing that can access higher-quality resin film or coating is provided.
In order to solve above-mentioned problem, the Biodegradable water soluble polyester compound of the 1st invention is the Biodegradable water soluble polyester compound that the emulsification of polyester biodegradable plastic is formed with emulsifying agent, and wherein the carboxylic acid in the polyester biodegradable plastic neutralizes with alkaline matter.
Emulsifying agent preferably contains the material (the 2nd invention) of nonionic surfactant 20～100 weight %.In addition, nonionic surfactant preferred molecular weight (the 3rd invention) below 3000.
Alkaline matter preferably has the material (the 4th invention) of pH pooling feature, is suitable for using hydroxycarboxylic acid an alkali metal salt (the 5th invention).
The Biodegradable polyester family macromolecule compound that the polyester biodegradable plastic that uses among the present invention uses before being always can contain residual (unreacted) monomer and/or oligopolymer, and the end of these monomers, oligopolymer or polymkeric substance has carboxyl.
As specific examples, can exemplify hydroxyl alkane acid or the homopolymer of 6-caprolactone or the multipolymers of these materials such as lactic acid, hydroxybutyric acid, hydroxypentanoic acid, oxysuccinic acid, oxyacetic acid.
In addition, also can use the succsinic acid of the terminal polymers of carboxylic acid of succsinic acid and ethylene glycol and/or butyleneglycol, the residual monomer that contains these or terminal carboxylic acid oligopolymer and the terminal alcohol multipolymer of ethylene glycol and/or butyleneglycol.
Among the present invention, the carboxylic acid in these polyester biodegradable plastics is neutralized with alkaline matter, make the pH of water soluble polyester compound preferably reach about 3.5～7.That is to say, said neutralization not only comprises and alkaline matter and carboxylic acid is reacted make system to reach the situation of the point of neutralization among the present invention, also comprises near situation about reaching the point of neutralization, even when reaching the point of neutralization in addition, pH also not necessarily reaches 7, and this situation is also included within the scope of the present invention.
Alkaline matter as neutralization is used except that general alkaline matter such as sodium hydroxide, yellow soda ash, ammoniacal liquor, triethylamine, trolamine, can also use Sodium phosphate dibasic or aminosaccharide.As aminosaccharide, for example the amine modifier of carboxymethyl cellulose, 2-amino-beta--modified sugars, polyoses such as D-glucopyranoside, wherein from the viewpoint of security, preferred D-glucosamine, D-galactosamine, chitosan etc. come from the biomass amine of organism.But in order to improve Long-term Storage stability, be particularly suitable for using having the pH pooling feature, can make the pH temperature of emulsion remain on hydroxycarboxylate in 3.5～7 the scope.As the example, the material that acid such as oxyacetic acid, lactic acid, oxysuccinic acid, citric acid, tartrate are obtained with basic metal such as sodium neutralizations for example, wherein Sodium.alpha.-hydroxypropionate, Trisodium Citrate, sodium tartrate are safe, even can be used as foodstuff additive and use, and can widen the purposes of emulsion.
The emulsifying agent that uses among the present invention preferably contains nonionic surfactant 20～100 weight %, more preferably contains 50～100 weight %.Contain nonionic surfactant by use like this and reach emulsifying agent more than the specified quantitative, can suppress the influence of ionic surfactant to pH, and the hydroxycarboxylic acid an alkali metal salt that has the pH pooling feature by use as mentioned above etc. carries out pH regulator as alkaline matter, can obtain the Long-term Storage stability under slightly acidic or neutrallty condition.
In addition, the preferred lower molecular weight of nonionic surfactant, preferred molecular weight (Mw) is below 3000, more preferably below 1500.In the prior art, exist tensio-active agent in time through ooze out problems such as producing unfavorable condition at coatingsurface, but by using low-molecular-weight emulsifying agent, major part moves to the surface when emulsion is dry, can be removed by once washing, therefore can access resin film or coating impure hardly, that have excellent water-resistance.
As the example of nonionic surfactant, for example Voranol EP 2001 class, polyoxyethylene alkyl phenyl ether class, polyoxyethylene alkyl amine ether, polyoxyethylene fatty acid ester, fatty acid esters of sorbitan, Vykamol Sorbitol 8B, sucrose fatty ester etc.Wherein, preferred polyoxyethylene lauryl ether or Vykamol Sorbitol 8B etc.
In the emulsifying agent that the present invention uses, except that above-mentioned nonionic surfactant, also can use the various ionic surfactants of anionic property, cationic or amphoteric.
As anionic surfactant's example, for example alkyl-sulphate, polyoxyethylene alkyl ether sulfate salt, sulfosuccinate, N-acyl amino hydrochlorate, carboxylate salt, sulfonate, phosphoric acid ester etc.In addition, as the example of cationic surfactant, alkylammonium salt for example, as amphoterics, for example alkyl (amido) betaine, alkyl-dimethyl amine oxide etc.
The consumption of mentioned emulsifier is 0.2～20 weight part (being converted into solids constituent here) with respect to polyester biodegradable plastic 100 weight parts usually.
Use emulsifying agent with the not special qualification of polyester biodegradable plastic emulsive concrete grammar, can adopt previously used general emulsification method.
For example can adopt that the polyester biodegradable plastic is dissolved in can be with in its dissolved solvent, add emulsifying agent after, slowly add the method for entry.Wherein, as solvent, can use for example ketones solvent such as butanone, chlorinated solvents such as aromatic series kind solvent, methylene dichloride such as esters solvents such as ethyl acetate, toluene etc.
Perhaps also can adopt the polyester biodegradable plastic is dissolved in above-mentioned solvent after, add emulsifier aqueous solution, make it one and be issued to phase inversion point, the method for dilute with water afterwards; And the polyester biodegradable plastic is warming up to its melt temperature, behind the blending emulsifiers, add warm water and carry out emulsive method etc.
Adopt Biodegradable water soluble polyester compound of the present invention,, can form the high quality thin film or the coating that contain impurity hardly by flooding or being coated on the fibre products such as paper or cloth and silk.More particularly,, it is coated in forms coating on the paper, can access the food product containers material of anti-electric furnace heating if be the emulsion of the poly(lactic acid) of advantage with the high-melting-point.
Embodiment
Below list embodiments of the invention, but the present invention is not subjected to the qualification of these embodiment.(embodiment 1)
To polylactic resin (Shimadzu Seisakusho Ltd.'s system (strain), LACTY9030, below identical) 50 parts be dissolved in 200 parts of solution that obtain of toluene and add Vykamol Sorbitol 8B (EO:20mol, molecular weight about 1200) 3 parts and sulfo-succinic acid dioctyl sodium salt are 3 parts, under the stirring of homodisperse device, after slowly adding 55 parts in water and making emulsified body, remove toluene under the reduced pressure.For the emulsified body that obtains, use 3.7 parts of Sodium.alpha.-hydroxypropionate 50% aqueous solution to carry out pH and adjust, (solids component is about 50%, particle diameter 0.8 μ m, pH3.8) 115 parts to obtain the aqueous emulsification of gonorrhoea.
In addition, in following each embodiment and comparative example, polylactic resin and present embodiment 1 take to be dissolved in emulsification behind the toluene, the operation of removing toluene after the emulsification under reduced pressure equally.(embodiment 2)
Except that using 10 parts of Sodium.alpha.-hydroxypropionate 50% aqueous solution to carry out pH adjusts, similarly to Example 1, (solids component is about 50%, particle diameter 0.8 μ m, pH5.5) 122 parts to obtain the aqueous emulsification of gonorrhoea of polylactic resin.(embodiment 3)
In 50 parts of polylactic resin, add polyoxyethylene lauryl ether (EO:18mol, molecular weight 978) 5 part, under the stirring of homodisperse device, after slowly adding 51 parts in water and making emulsified body, carrying out pH with 5 parts of Sodium phosphate dibasic 10% aqueous solution adjusts, (solids component is about 50%, particle diameter 2.5 μ m, pH4.1) 111 parts to obtain the aqueous emulsification of gonorrhoea.(embodiment 4)
In 50 parts of polylactic resin, add polyoxyethylene lauryl ether (EO:18mol, molecular weight 978) 5 part, under the stirring of homodisperse device, after slowly adding 46.1 parts in water and making emulsified body, carrying out pH with 11 parts of Sodium phosphate dibasic 10% aqueous solution adjusts, (solids component is about 50%, particle diameter 2.5 μ m, pH6.1) 112 parts to obtain the aqueous emulsification of gonorrhoea.(embodiment 5)
In 50 parts of polylactic resin, add in 0.3 part of the triethylamine and behind the carboxylic acid, add polyoxyethylene lauryl ether (EO:18mol) 5 parts, under the stirring of homodisperse device, slowly add 55 parts in water, (solids component is about 50%, particle diameter 1.5 μ m, pH4.0) 110 parts to obtain the aqueous emulsification of gonorrhoea.(embodiment 6)
In 50 parts of polylactic resin, add polyoxyethylene lauryl ether (EO:18mol, molecular weight 978) 5 part, under the stirring of homodisperse device, after slowly adding 51 parts in water and making emulsified body, with 3.9 parts of neutralizations of 5% aqueous sodium hydroxide solution, (solids component is about 50%, particle diameter 2.5 μ m, pH6.8) 110 parts to obtain the aqueous emulsification of gonorrhoea.(comparative example 1)
Add 5 parts of polyoxyethylene lauryl ether (EO:18mol) in 50 parts of polylactic resin, under the stirring of homodisperse device, slowly add 55 parts in water, (solids component is about 50%, particle diameter 1.2 μ m, pH2.2) 110 parts to obtain the aqueous emulsification of gonorrhoea.(comparative example 2)
Add 8.3 parts of Sodium Lauryl Sulphate BP/USP 30% aqueous solution in 50 parts of polylactic resin, under the stirring of homodisperse device, slowly add 47 parts in water, (solids component is about 50%, particle diameter 1.9 μ m, pH3.8) 105 parts to obtain the aqueous emulsification of gonorrhoea.
For the emulsification that the foregoing description and comparative example obtain, investigate A-stage and the 40 ℃ pH after 1 week of storage, 2 weeks, 4 weeks down, according to following standard evaluation storage stability.The result is as shown in table 1.40 ℃ of storages promote the storage stability evaluation of test:
◎: pH is stable in 4 weeks, confirms the segregation that does not have water in appearance at emulsion
Zero: pH changes, and confirms the segregation that does not have water in appearance at emulsion
Or pH is stable, but confirms to have in appearance at emulsion the segregation of some water
*: confirm at the significant water isolation table 1 of having in appearance of emulsion
The invention effect
According to the present invention, the hydrolysis after the water system that can be inhibited, life that can Long-term Storage The thing degradability water soluble polyester compound. Particularly the 2nd invention of the present invention can suppress ionic Surfactant is to the impact of pH, the storage-stable height.
In addition, according to the 3rd invention, can access the high-quality resin film that does not contain impurity.
And the 4th, 5 invention can keep pH stable by its pH pooling feature, and be long-term Storage-stable is especially good.
Claims (5)
1, Biodegradable water soluble polyester compound, be with emulsifying agent with the Biodegradable water soluble polyester compound that the emulsification of polyester biodegradable plastic forms, it is characterized in that the carboxylic acid in the polyester biodegradable plastic neutralizes with alkaline matter.
2, Biodegradable water soluble polyester compound as claimed in claim 1 is characterized in that, mentioned emulsifier is the material that contains 20～100 weight % nonionic surfactants.
3, Biodegradable water soluble polyester compound as claimed in claim 2 is characterized in that, the molecular weight of above-mentioned nonionic surfactant is below 3000.
4, as any described Biodegradable water soluble polyester compound in the claim 1～3, it is characterized in that above-mentioned alkaline matter is the material with pH pooling feature.
5, Biodegradable water soluble polyester compound as claimed in claim 4 is characterized in that, the alkaline matter of the above-mentioned pH of having pooling feature is the hydroxycarboxylic acid an alkali metal salt.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP234082/2001 | 2001-08-01 | ||
| JP2001234082 | 2001-08-01 | ||
| JP2002179134A JP3685157B2 (en) | 2001-08-01 | 2002-06-19 | Biodegradable polyester water-based product that can be stored for a long time |
| JP179134/2002 | 2002-06-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1400247A true CN1400247A (en) | 2003-03-05 |
| CN1234768C CN1234768C (en) | 2006-01-04 |
Family
ID=26619794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021271437A Expired - Fee Related CN1234768C (en) | 2001-08-01 | 2002-07-25 | Biodegradable water soluble polyester compound capable of being stored for long time |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3685157B2 (en) |
| KR (1) | KR100485491B1 (en) |
| CN (1) | CN1234768C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748509B (en) * | 2008-12-05 | 2012-06-06 | 东丽纤维研究所（中国）有限公司 | Polylactic acid fiber with high hydrolytic resistance performance |
| CN101608350B (en) * | 2008-06-20 | 2012-07-25 | 东丽纤维研究所（中国）有限公司 | Polylactic fiber with high hydrolytic resistance |
| CN101910309B (en) * | 2008-03-25 | 2013-06-19 | 东丽纤维研究所（中国）有限公司 | Polylactic acid composition, and film comprising the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8247157B2 (en) * | 2008-12-09 | 2012-08-21 | Xerox Corporation | Toner process |
| US8460848B2 (en) * | 2010-12-14 | 2013-06-11 | Xerox Corporation | Solvent-free bio-based emulsion |
| PL3423512T3 (en) | 2016-02-29 | 2022-03-14 | Michelman, Inc. | Aqueous-based hydrolytically stable dispersion of a biodegradable polymer |
-
2002
- 2002-06-19 JP JP2002179134A patent/JP3685157B2/en not_active Expired - Fee Related
- 2002-07-23 KR KR10-2002-0043168A patent/KR100485491B1/en not_active IP Right Cessation
- 2002-07-25 CN CNB021271437A patent/CN1234768C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910309B (en) * | 2008-03-25 | 2013-06-19 | 东丽纤维研究所（中国）有限公司 | Polylactic acid composition, and film comprising the same |
| CN101608350B (en) * | 2008-06-20 | 2012-07-25 | 东丽纤维研究所（中国）有限公司 | Polylactic fiber with high hydrolytic resistance |
| CN101748509B (en) * | 2008-12-05 | 2012-06-06 | 东丽纤维研究所（中国）有限公司 | Polylactic acid fiber with high hydrolytic resistance performance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003113247A (en) | 2003-04-18 |
| KR20030011604A (en) | 2003-02-11 |
| KR100485491B1 (en) | 2005-04-28 |
| JP3685157B2 (en) | 2005-08-17 |
| CN1234768C (en) | 2006-01-04 |
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