JPH0593030A - Biodegradable polymeric material - Google Patents
Biodegradable polymeric materialInfo
- Publication number
- JPH0593030A JPH0593030A JP3280502A JP28050291A JPH0593030A JP H0593030 A JPH0593030 A JP H0593030A JP 3280502 A JP3280502 A JP 3280502A JP 28050291 A JP28050291 A JP 28050291A JP H0593030 A JPH0593030 A JP H0593030A
- Authority
- JP
- Japan
- Prior art keywords
- polymer material
- hydroxyl group
- weight
- natural
- natural polymer
- 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
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- -1 polyol compound Chemical class 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000002861 polymer material Substances 0.000 claims description 31
- 229920005615 natural polymer Polymers 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 229920002988 biodegradable polymer Polymers 0.000 claims description 12
- 239000004621 biodegradable polymer Substances 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 238000010559 graft polymerization reaction Methods 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 3
- 229930014626 natural product Natural products 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 9
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract description 2
- 229920002678 cellulose Polymers 0.000 abstract 1
- 239000001913 cellulose Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 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 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- AMJYHMCHKZQLAY-UHFFFAOYSA-N tris(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound O=C=NC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)N=C=O)OC1=CC=CC=C1N=C=O AMJYHMCHKZQLAY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/06—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules
- C08F291/08—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules on to macromolecules containing hydroxy radicals
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、生分解性高分子材料及
びその製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a biodegradable polymer material and a method for producing the same.
【０００２】[0002]
【従来の技術及びその問題点】これまでに生産されてき
た合成高分子は、古くから存在する天然高分子とは異な
り、自然の循環システムには組み入れにくいため、廃棄
プラスチックは地球環境の劣化を引き起こし大きな問題
となっている。一方、綿、麻、木材、でんぷん等の植物
性成分は廃棄されれば土壌中の微生物によって自然に分
解され、再び炭酸ガスや肥料として植物に取り込まれ
る。[Prior Art and its Problems] Unlike the natural polymers that have existed since ancient times, the synthetic polymers that have been produced so far are difficult to incorporate into the natural circulation system, so waste plastics do not deteriorate the global environment. Causing a big problem. On the other hand, when plant components such as cotton, hemp, wood, and starch are discarded, they are naturally decomposed by microorganisms in the soil and are again taken into the plant as carbon dioxide and fertilizer.
【０００３】本発明者らは、合成高分子に生分解性を付
与する方法を鋭意研究中のところ、植物成分を分子中に
組み込んだタイプの高分子材料が微生物によって分解さ
れるとともに、すぐれた物性を有することを見出した。
このようなタイプの生分解性高分子材料は従来全く知ら
れていない。本発明による生分解性高分子材料はプラス
チック廃棄物による地球環境問題を解決するための有効
な手段となり得るものである。The inventors of the present invention have been earnestly researching a method for imparting biodegradability to a synthetic polymer, and a polymer material of a type in which a plant component is incorporated into a molecule is decomposed by a microorganism and is excellent. It was found to have physical properties.
No biodegradable polymer material of this type has hitherto been known. The biodegradable polymer material according to the present invention can be an effective means for solving the global environmental problems caused by plastic waste.
【０００４】[0004]
【発明が解決しようとする課題】そこで、本発明は、生
分解性を有する新規な高分子材料及びその製造方法を提
供することをその課題とする。Therefore, an object of the present invention is to provide a novel polymer material having biodegradability and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】本発明によれば、ヒドロ
キシル基を含有する固体状天然高分子材料に対して、そ
のヒドロキシル基を介してポリウレタン鎖を反応結合さ
せてたものからなり、該ポリウレタン鎖の結合量が天然
高分子材料に対して１０重量％以上であることを特徴と
する生分解性高分子材料が提供される。また、本発明に
よれば、ヒドロキシル基を含有する固体状天然高分子材
料を、イソシアネート化合物とポリオール化合物を含む
反応溶液と接触反応させることからなり、該イソシアネ
ート化合物とポリオール化合物の合計反応重量が、該天
然高分子材料に対して１０重量％以上であることを特徴
とする生分解性高分子材料の製造方法が提供される。さ
らに、本発明によれば、ヒドロキシル基を含有する固体
状天然高分子材料に対して、そのヒドロキシル基の存在
に起因する活性点を介してビニルモノマーをグラフト重
合させたものからなり、該ビニルモノマーの重合体の結
合量が、該固体状天然高分子材料に対して１０重量％以
上であることを特徴とする生分解性高分子材料が提供さ
れる。さらにまた、本発明によれば、ヒドロキシル基を
含有する固体状高分子材料をビニルモノマー及びグラフ
ト重合触媒を含む溶液を接触反応させることからなり、
該ビニルモノマーの反応重量が、該天然高分子材料に対
して１０重量％以上である生分解性高分子材料の製造方
法が提供される。According to the present invention, a solid natural polymer material containing a hydroxyl group is obtained by reacting a polyurethane chain through the hydroxyl group, the polyurethane comprising There is provided a biodegradable polymer material characterized in that the amount of chains bonded is 10% by weight or more based on the natural polymer material. Further, according to the present invention, a solid natural polymer material containing a hydroxyl group, which comprises reacting with a reaction solution containing an isocyanate compound and a polyol compound, the total reaction weight of the isocyanate compound and the polyol compound, There is provided a method for producing a biodegradable polymer material, which is 10% by weight or more based on the natural polymer material. Further, according to the present invention, a solid natural polymer material containing a hydroxyl group is obtained by graft-polymerizing a vinyl monomer via an active site due to the presence of the hydroxyl group. Provided is a biodegradable polymer material, characterized in that the amount of the polymer bound is 10% by weight or more based on the solid natural polymer material. Furthermore, according to the present invention, a solid polymer material containing a hydroxyl group is contacted with a solution containing a vinyl monomer and a graft polymerization catalyst,
Provided is a method for producing a biodegradable polymer material, wherein the reaction weight of the vinyl monomer is 10% by weight or more based on the natural polymer material.
【０００６】本発明で用いる天然高分子材料は、ヒドロ
キシル基を含有する固体状、例えば、粉末状、フィルム
状、板状、ブロック状、ペレット状、繊維状のものであ
るヒドロキシル基を含有する。天然高分子材料の具体例
としては、セルロース系物質、ヘシセルロース系物質、
リグノセルロース系物質、リグニン系物質、でん粉系物
質等を挙げることができる。本発明によれば、これらの
天然高分子材料は、その固体状態を保持したまま、モノ
マー成分と反応させる。The natural polymer material used in the present invention contains a hydroxyl group-containing solid form, for example, a powder form, a film form, a plate form, a block form, a pellet form, or a fibrous form. Specific examples of natural polymer materials include cellulosic substances, hecicellulose-based substances,
Examples thereof include lignocellulosic materials, lignin-based materials, starch-based materials and the like. According to the invention, these natural polymeric materials are reacted with the monomer components while retaining their solid state.
【０００７】本発明の第１の方法においては、天然高分
子材料は、これにポリイソシアネート化合物とポリオー
ル化合物を含有する溶液と接触反応させて、ポリウレタ
ン鎖を結合させた高分子材料とする。このポリウレタン
鎖の結合量は、天然高分子材料に対して、１０重量％以
上、好ましくは１５〜３００重量％である。In the first method of the present invention, the natural polymeric material is brought into contact with a solution containing a polyisocyanate compound and a polyol compound, to obtain a polymeric material having polyurethane chains bonded thereto. The amount of the polyurethane chains bound is 10% by weight or more, preferably 15 to 300% by weight, based on the natural polymer material.
【０００８】ポリイソシアネートとしては、脂肪族系ポ
リイソシアネート、脂環族系ポリイソシアネートおよび
芳香族系ポリイソシアネートの他、それらの変性体が包
含される。脂肪族系ポリイソシアネートとしては、例え
ば、ヘキサメチレンジイソシアネートが挙げられ、脂環
族系ポリイソシアネートとしては、例えば、イソホロン
ジイソシアネートが挙げられる。芳香族系ポリイソシア
ネートとしては、例えば、トリレンジイソシアネート、
キシリレンジイソシアネート、ジフェニルメタンジイソ
シアネート、ポリメリックジフェニルメタンジイソシア
ネート、トリフェニルメタントリイソシアネート、トリ
ス（イソシアネートフェニル）チオホスフェート等が挙
げられる。ポリイソシアネート変性体としては、例え
ば、ウレタンプレポリマー、ヘキサメチレンジイソシア
ネートビューレット、ヘキサメチレンジイソシアネー
ト、トリマー、イソホロンジイソシアネートトリマー等
が挙げられる。Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified products thereof. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, and examples of the alicyclic polyisocyanate include isophorone diisocyanate. As the aromatic polyisocyanate, for example, tolylene diisocyanate,
Examples thereof include xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tris (isocyanatophenyl) thiophosphate. Examples of the modified polyisocyanate include urethane prepolymer, hexamethylene diisocyanate burette, hexamethylene diisocyanate, trimer, and isophorone diisocyanate trimer.
【０００９】ポリオール化合物としては、ポリウレタン
の製造に用いられる各種のものが用いられ、このような
ものとしては、例えば、エチレングリコール、ジエチレ
ングリコール、１，４−ブタンジオール、１，６−ヘキ
サンジオール、ネオペンチルグリコール、トリメチロー
ルプロパン、グリセリン、トリエタノールアミン、ソル
ビトール等の低分子量ポリオール；ポリエチレングリコ
ール、ポリプロピレングリコール、ポリテトラメチレン
グリコール、エチレンオキシド／プロピレンオキシド共
重合体等のポリエーテルポリオール；ポリカプロラクト
ン、ポリβ−メチル−δ−ブチロラクトン、ジオールと
二塩基酸からのポリエステル等が挙げられる。その他、
水酸基含有液状ポリブタジエン、ポリカーボネートジオ
ール、アクリルポリオール等が挙げられる。As the polyol compound, various compounds used in the production of polyurethane are used. Examples of such compounds include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol and neo. Low molecular weight polyols such as pentyl glycol, trimethylolpropane, glycerin, triethanolamine, sorbitol; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide / propylene oxide copolymers; polycaprolactone, poly β- Examples include methyl-δ-butyrolactone, polyesters from diols and dibasic acids, and the like. Other,
Examples thereof include hydroxyl group-containing liquid polybutadiene, polycarbonate diol, acrylic polyol, and the like.
【００１０】ポリイソアネ−ト化合物及びポリオ−ル化
合物を含有する反応溶液には、慣用の触媒、例えば、ス
ズ系やアミン系の触媒を含有させることができる。ポリ
イソアネ−ト化合物の使用割合は、ポリオ−ル化合物及
び天然高分子材料中に含まれる全ヒドロキシル基の当量
数に対しそのイソシアネ−ト基当量数で０．８〜２．０
倍当量、好ましくは１．０〜１．５倍当量である。ま
た、ポリイソシアネ−ト化合物とポリオ−ル化合物の合
計反応量は天然高分子材料に対し１０重量％以上、好ま
しくは１５〜３００重量％である。天然高分子材料にた
いしてポリイソシアネ−ト化合物及びポリオ−ル化合物
からなる反応溶液を接触反応させる場合、その反応温度
は１０〜１５０℃、好ましくは２０〜１２０℃である。The reaction solution containing the polyisocyanate compound and the polyol compound may contain a conventional catalyst, for example, a tin-based or amine-based catalyst. The proportion of the polyisocyanate compound used is 0.8 to 2.0 in terms of the equivalent number of the isocyanate group to the equivalent number of all the hydroxyl groups contained in the polyol compound and the natural polymer material.
It is a double equivalent, preferably 1.0 to 1.5 times equivalent. The total reaction amount of the polyisocyanate compound and the polyol compound is 10% by weight or more, preferably 15 to 300% by weight, based on the natural polymer material. When a reaction solution containing a polyisocyanate compound and a polyol compound is contact-reacted with a natural polymer material, the reaction temperature is 10 to 150 ° C, preferably 20 to 120 ° C.
【００１１】本発明の第２の方法においては、天然高分
子材料に対し、ビニルモノマ−をグラフト重合させ、重
合体鎖を結合させた高分子材料とする。この重合体鎖
は、天然高分子材料に対して１０重量％以上、好ましく
は１５〜３００重量％である。ビニルモノマーとして
は、エチレン、プロピレン、ブテン、ブタジエン等のオ
レフィンの他、酢酸ビニル、スチレン、塩化ビニル、ア
クリロニトリル、フッ化ビニル、アクリル酸エステル、
メタクリル酸エステル等が挙げられる。天然高分子材料
にビニルモノマーをグラフト重合させる方法としては、
ビニルモノマー溶液を、天然高分子材料に接触反応させ
る。ビニルモノマー溶液には、慣用のグラフト重合触
媒、例えば、Ｃｅ4+、Ｆｅ2+ − Ｈ2Ｏ2系等の触媒を含
有させる。ビニルモノマーを溶解させる溶媒として、慣
用のもの、例えば、水、メタノール等が挙げられる。反
応温度は０〜１００℃、好ましくは１０〜８０℃であ
る。ビニルモノマーの反応重量は、天然高分子材料に対
して１０重量％以上、好ましくは１５〜３００重量％で
ある。In the second method of the present invention, a vinyl polymer is graft-polymerized to a natural polymer material to obtain a polymer material in which polymer chains are bonded. This polymer chain is 10% by weight or more, preferably 15 to 300% by weight, based on the natural polymer material. As vinyl monomers, in addition to olefins such as ethylene, propylene, butene, butadiene, vinyl acetate, styrene, vinyl chloride, acrylonitrile, vinyl fluoride, acrylic acid ester,
Methacrylic acid ester and the like can be mentioned. As a method of graft-polymerizing a vinyl monomer on a natural polymer material,
The vinyl monomer solution is catalytically reacted with the natural polymer material. The vinyl monomer solution contains a conventional graft polymerization catalyst, for example, a catalyst such as Ce 4 +, Fe 2 + -H 2 O 2 system. As the solvent for dissolving the vinyl monomer, a conventional solvent such as water or methanol can be used. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. The reaction weight of the vinyl monomer is 10% by weight or more, preferably 15 to 300% by weight, based on the natural polymer material.
【００１２】[0012]
【発明の効果】本発明により得られる天然高分子材料に
ポリウレタン鎖やビニルモノマーの重合体鎖が結合した
高分子材料は、その基幹高分子が天然高分子材料である
ことから、すぐれた微生物分解性を有するものであり、
また、その基幹高分子である天然高分子材料には、ポリ
ウレタン鎖やビニルモノマーの重合体鎖が結合している
ことから、機械的強度において著しく向上したものであ
る。本発明の生分解性高分子材料は、フィルム状、シー
ト状、ブロック状、繊維状、粉末状等の任意の形状で用
いられる。粉末状のものは、熱可塑性樹脂に対する充填
剤として用いることができる。EFFECT OF THE INVENTION The natural polymer material obtained by the present invention has a polyurethane polymer or a polymer chain of vinyl monomer bonded to it. That has
Further, the natural polymer material, which is the basic polymer, has a polyurethane chain or a polymer chain of a vinyl monomer bonded thereto, so that the mechanical strength is remarkably improved. The biodegradable polymer material of the present invention is used in any shape such as film, sheet, block, fiber and powder. The powdery one can be used as a filler for the thermoplastic resin.
【００１３】[0013]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。 実施例１ ブナチップをクレゾール／水混合溶液（容量混合比＝８
／２）中において１８０℃で５時間蒸解した後のクレゾ
ール層から分離精製したソルボルシスリグニン（ＳＬ）
１５０重量部を、テトラヒドロフラン（ＴＨＦ）１５０
重量部に溶解させた。この溶液２４０重量部とポリメリ
ックジフェニルメタンジイソシアネート（ＭＤＩ）１０
０重量部を撹拌混合して反応溶液を得た。次に、この反
応溶液に天然高分子材料としての定性濾紙を浸漬し、反
応溶液を十分に含浸させた後、風乾し、得られた風乾物
をステンレス板の間に置き、１１５℃で４時間加熱して
反応させ、シート状物（ポリウレタン鎖の結合した濾
紙）を得た。また、前記と同様にして、濾紙に対するポ
リウレタン結合量（重量％）が種々異ったシート状物を
得た。前記のようにして得たシート状物について、その
応力−ヒズミ曲線を測定した。その結果を次表に示す。EXAMPLES Next, the present invention will be described in more detail by way of examples. Example 1 Beech chips were mixed with cresol / water mixed solution (volume mixing ratio = 8).
/ 2) sorborsis lignin (SL) separated and purified from the cresol layer after digestion at 180 ° C for 5 hours
150 parts by weight of tetrahydrofuran (THF) 150
It was dissolved in 1 part by weight. 240 parts by weight of this solution and 10 parts of polymeric diphenylmethane diisocyanate (MDI)
0 parts by weight was mixed with stirring to obtain a reaction solution. Next, a qualitative filter paper as a natural polymer material was dipped in this reaction solution, sufficiently impregnated with the reaction solution, and then air-dried. The obtained air-dried product was placed between stainless plates and heated at 115 ° C. for 4 hours. And reacted to obtain a sheet-like material (polyurethane chain-bonded filter paper). Further, in the same manner as described above, sheet-like materials having various amounts (% by weight) of polyurethane bonded to the filter paper were obtained. The stress-strain curve of the sheet-like material obtained as described above was measured. The results are shown in the table below.
【００１４】[0014]
【表１】 [Table 1]
【００１５】実施例２ 実施例１で示したＳＬ１００重量部と分子量４００のポ
リプロピレングリコール（ＰＰＧ）１００重量部をＴＨ
Ｆ１００重量部に溶解させて溶液を作り、この溶液２０
０重量部にＭＤＩ１００重量部を撹拌混合して反応溶液
を得た。この反応溶液を用いて、実施例１と同様にして
ポリウレタン鎖を有するシート状物を得た。このように
して得たシート状物について、その応力−ヒズミ曲線を
測定した。その結果を表２に示す。Example 2 100 parts by weight of SL shown in Example 1 and 100 parts by weight of polypropylene glycol (PPG) having a molecular weight of 400 were added to TH.
A solution is prepared by dissolving it in 100 parts by weight of F.
100 parts by weight of MDI was mixed with 0 parts by weight with stirring to obtain a reaction solution. Using this reaction solution, a sheet having a polyurethane chain was obtained in the same manner as in Example 1. The stress-strain curve of the sheet-like material thus obtained was measured. The results are shown in Table 2.
【００１６】[0016]
【表２】 [Table 2]
【００１７】実施例３ 実施例１において、ＳＬの代りにオタール蒸留残渣（Ｗ
Ｔ）を用いて以外は同様にしてシート状物を得た。この
シート状物について、その応力−ヒズミ曲線を測定し
た。その結果を表３に示す。Example 3 In Example 1, instead of SL, an otar distillation residue (W
A sheet-like material was obtained in the same manner except that T) was used. The stress-strain curve of this sheet-shaped material was measured. The results are shown in Table 3.
【００１８】[0018]
【表３】 [Table 3]
【００１９】実施例４ 実施例２において、ＳＬの代りにＷＴを用いた以外は同
様にしてシート状物を得た。このシート状物について、
その応力−ヒズミ曲線を測定した。その結果を表４に示
す。Example 4 A sheet-like material was obtained in the same manner as in Example 2 except that WT was used instead of SL. About this sheet
The stress-strain curve was measured. The results are shown in Table 4.
【００２０】[0020]
【表４】 [Table 4]
Claims (5)
分子材料に対して、そのヒドロキシル基を介してポリウ
レタン鎖を反応結合させてたものからなり、該ポリウレ
タン鎖の結合量が天然高分子材料に対して１０重量％以
上であることを特徴とする生分解性高分子材料。1. A solid natural polymer material containing a hydroxyl group in which a polyurethane chain is reactively bonded through the hydroxyl group, and the amount of the polyurethane chain bonded to the natural polymer material is 1. On the other hand, a biodegradable polymer material characterized by being 10% by weight or more.
分子材料を、ポリイソシアネート化合物とポリオール化
合物を含む反応溶液と接触反応させることからなり、該
イソシアネート化合物とポリオール化合物の合計反応重
量が、該天然高分子材料に対して１０重量％以上である
ことを特徴とする生分解性高分子材料の製造方法。2. A solid natural polymer material containing a hydroxyl group is contact-reacted with a reaction solution containing a polyisocyanate compound and a polyol compound, and the total reaction weight of the isocyanate compound and the polyol compound is the natural product. A method for producing a biodegradable polymer material, which comprises 10% by weight or more of the polymer material.
性のヒドロキシル基含有天然高分子を用いる請求項２の
方法。3. The method according to claim 2, wherein a soluble hydroxyl group-containing natural polymer is used as a part of the polyol compound.
分子材料に対して、そのヒドロキシル基の存在に起因す
る活性点を介してビニルモノマーをグラフト重合させた
ものからなり、該ビニルモノマーの重合体の結合量が、
該固体状天然高分子材料に対して１０重量％以上である
ことを特徴とする生分解性高分子材料。4. A polymer of a vinyl monomer, which is obtained by graft-polymerizing a vinyl monomer onto a solid natural polymer material containing a hydroxyl group via an active site due to the presence of the hydroxyl group. The binding amount of
A biodegradable polymer material, which is 10% by weight or more based on the solid natural polymer material.
材料をビニルモノマー及びグラフト重合触媒を含む溶液
を接触反応させることからなり、該ビニルモノマーの反
応重量が、該天然高分子材料に対して１０重量％以上で
ある生分解性高分子材料の製造方法。5. A solid polymeric material containing a hydroxyl group is catalytically reacted with a solution containing a vinyl monomer and a graft polymerization catalyst, and the reaction weight of the vinyl monomer is 10 relative to the natural polymeric material. A method for producing a biodegradable polymer material, which comprises at least wt%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3280502A JP2611171B2 (en) | 1991-09-30 | 1991-09-30 | Biodegradable polymer material |
| GB9205892A GB2260138A (en) | 1991-09-30 | 1992-03-17 | Biodegradable composite material and process of producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3280502A JP2611171B2 (en) | 1991-09-30 | 1991-09-30 | Biodegradable polymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0593030A true JPH0593030A (en) | 1993-04-16 |
| JP2611171B2 JP2611171B2 (en) | 1997-05-21 |
Family
ID=17625987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3280502A Expired - Lifetime JP2611171B2 (en) | 1991-09-30 | 1991-09-30 | Biodegradable polymer material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2611171B2 (en) |
| GB (1) | GB2260138A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3008652U (en) * | 1994-09-06 | 1995-03-20 | 筒中プラスチック工業株式会社 | Seed sign |
| JPH07216203A (en) * | 1993-07-28 | 1995-08-15 | Samsung General Chem Co Ltd | Decomposable foam and method for producing the same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4317692C2 (en) * | 1993-05-27 | 1999-08-26 | Biotec Biolog Naturverpack | Process for the production of composite materials from renewable raw materials |
| DE4331747A1 (en) * | 1993-09-20 | 1995-03-23 | Wuenning Paul | Extruded, fiber-reinforced natural material granulate for thermoplastic processing, and process for its production |
| JP4250321B2 (en) * | 2000-10-17 | 2009-04-08 | キヤノン株式会社 | Method for producing resin composition, and method for producing molded body for processing resin composition obtained by the production method |
| WO2011100818A1 (en) | 2010-02-18 | 2011-08-25 | Fpinnovations | Thermoplastic nanocomposite material based on nanocrystalline cellulose (ncc) |
| WO2011147027A2 (en) * | 2010-05-26 | 2011-12-01 | Fpinnovations | Hydrophobic lignocellulosic material and process therefor |
| CN106493827B (en) * | 2016-10-12 | 2018-07-20 | 浙江农林大学 | A kind of engineered wood and preparation method thereof |
| CN110790889A (en) * | 2019-11-20 | 2020-02-14 | 苏州市雄林新材料科技有限公司 | Polarity-controllable TPU film and preparation method thereof |
| CN115417964B (en) * | 2022-09-21 | 2024-02-23 | 台州益普高分子材料有限公司 | Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2109686C3 (en) * | 1971-03-02 | 1980-09-25 | Bayer Ag, 5090 Leverkusen | Process for the production or refinement of materials containing lignocellulose |
| US3919017A (en) * | 1973-10-05 | 1975-11-11 | Ellingson Timber Company | Polyisocyanate:formaldehyde binder system for cellulosic materials |
| IT1008392B (en) * | 1974-03-07 | 1976-11-10 | Montedison Spa | PROCEDURE FOR THE ESTERIFICATION IN THE STEAM PHASE OF UNSATURATED ALPHA BETA SILICON ACIDS |
| GB1502979A (en) * | 1975-09-23 | 1978-03-08 | Ellingson Timber Co | Method of joining together bodies of cellulosic material |
| GB1585074A (en) * | 1977-05-16 | 1981-02-25 | Wadeson F P | Process for the manufacture of cellulose-polyurethane materials |
| US4197372A (en) * | 1978-01-16 | 1980-04-08 | Krause Milling Company | Semi-flexible polyurethane foams containing amylaceous material and process for preparing same |
| US4317752A (en) * | 1979-02-21 | 1982-03-02 | Blount David H | Process for the production of polyisocyanate lignin-cellulose plastics |
| GB2112791A (en) * | 1981-12-11 | 1983-07-27 | Epsilon Dev Ltd | Production of polyurethane from cellulose |
| US4521544A (en) * | 1983-02-24 | 1985-06-04 | Patrick J. Crehan | Polyurethane foam from cellulosic products |
| US4505778A (en) * | 1983-09-06 | 1985-03-19 | Ici Americas Inc. | Paper products sized with polyisocyanate blends |
| US4490517A (en) * | 1983-10-03 | 1984-12-25 | Olin Corporation | Solid TDI residue-dicarboxylic ester binder composition and lignocellulosic composite materials prepared therefrom |
| US4944823A (en) * | 1985-09-26 | 1990-07-31 | Carbocol, Inc. | Composition for bonding solid lignocellulosic materials |
| JP2675997B2 (en) * | 1988-05-16 | 1997-11-12 | 工業技術院長 | Novel polyurethane manufacturing method |
| GB8813396D0 (en) * | 1988-06-07 | 1988-07-13 | Earl H A | Composite materials |
-
1991
- 1991-09-30 JP JP3280502A patent/JP2611171B2/en not_active Expired - Lifetime
-
1992
- 1992-03-17 GB GB9205892A patent/GB2260138A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07216203A (en) * | 1993-07-28 | 1995-08-15 | Samsung General Chem Co Ltd | Decomposable foam and method for producing the same |
| JP3008652U (en) * | 1994-09-06 | 1995-03-20 | 筒中プラスチック工業株式会社 | Seed sign |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2611171B2 (en) | 1997-05-21 |
| GB2260138A (en) | 1993-04-07 |
| GB9205892D0 (en) | 1992-04-29 |
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