JP2000038595A - Water-soluble copolymer and detergent builder - Google Patents
Water-soluble copolymer and detergent builderInfo
- Publication number
- JP2000038595A JP2000038595A JP10225481A JP22548198A JP2000038595A JP 2000038595 A JP2000038595 A JP 2000038595A JP 10225481 A JP10225481 A JP 10225481A JP 22548198 A JP22548198 A JP 22548198A JP 2000038595 A JP2000038595 A JP 2000038595A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- water
- methylene
- acid
- pref
- 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.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 34
- 239000003599 detergent Substances 0.000 title claims description 10
- -1 cyclic ketene acetal Chemical class 0.000 claims abstract description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- AVUFZLGLMCACRE-UHFFFAOYSA-N 2-methylidene-1,3-dioxepane Chemical compound C=C1OCCCCO1 AVUFZLGLMCACRE-UHFFFAOYSA-N 0.000 abstract description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 abstract description 3
- VHMYBWIOLGKSHO-UHFFFAOYSA-N 2-methylidene-1,3-dioxolane Chemical compound C=C1OCCO1 VHMYBWIOLGKSHO-UHFFFAOYSA-N 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001530 fumaric acid Substances 0.000 abstract description 2
- 150000002560 ketene acetals Chemical class 0.000 abstract description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 2
- 239000011976 maleic acid Substances 0.000 abstract description 2
- PWKDHWCKSUMJID-UHFFFAOYSA-N 2-methylidene-1,3-dioxane Chemical compound C=C1OCCCO1 PWKDHWCKSUMJID-UHFFFAOYSA-N 0.000 abstract 1
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 8
- 238000006065 biodegradation reaction Methods 0.000 description 8
- 239000004927 clay Substances 0.000 description 8
- 239000004584 polyacrylic acid Substances 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000003405 preventing effect Effects 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 102100029777 Eukaryotic translation initiation factor 3 subunit M Human genes 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 101001012700 Homo sapiens Eukaryotic translation initiation factor 3 subunit M Proteins 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
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 101001094026 Synechocystis sp. (strain PCC 6803 / Kazusa) Phasin PhaP Proteins 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は生分解性を有し洗剤
ビルダーとして有用な水溶性共重合体に関するものであ
り、さらに該水溶性共重合体は顔料分散剤、石炭水スラ
リー分散剤、セメント分散剤、農薬分散剤、スケール防
止剤などにも利用可能なものであるので、本発明は、そ
れら各種薬剤の製造および応用技術に属するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble copolymer which is biodegradable and is useful as a detergent builder. The water-soluble copolymer further comprises a pigment dispersant, a coal water slurry dispersant, and a cement dispersant. Since the present invention can be used as a dispersant, a pesticide dispersant, a scale inhibitor, and the like, the present invention belongs to the production and application techniques of these various drugs.
【０００２】[0002]
【従来の技術】従来、界面活性剤を主成分とする洗浄剤
においては、該界面活性剤の補助成分としてビルダーを
配合することにより、洗浄性能を高めることがおこなわ
れている。すなわち、水中にはカルシウムイオンやマグ
ネシウムイオンなどの多価金属イオンが通常存在してお
り、これらは界面活性剤と結合すると水に不溶の金属塩
を形成し洗浄力を低下させる。洗剤ビルダーは、このよ
うな多価金属イオンと結合して発生する界面活性剤の洗
浄力低下を防ぐためのものである。さらに洗剤ビルダー
には、このような金属イオン封鎖作用に加えて、再汚染
防止作用等の分散作用やアルカリ緩衝作用も要求とされ
ている。これらの要求を満たす洗剤ビルダーとして、ナ
トリウムやカリウムの炭酸塩、炭酸水素塩、リン酸塩、
ポリリン酸塩、ケイ酸塩あるいはゼオライトなどの無機
化合物や、ポリアクリル酸、ポリマレイン酸、ポリイタ
コン酸などの不飽和カルボン酸の重合体などが知られて
いる。これらのビルダーの中では、性能、安全性、価格
の面から、リン酸塩、ポリリン酸塩が広く使用されてき
たが、これらのリン化合物は、河川や湖沼の富栄養化の
原因となるため現在ではその使用が制限されており、そ
の代替物として、ゼオライトや不飽和カルボン酸重合体
などが提供されているが、ゼオライトは水に対する溶解
度が小さく河川や湖沼に堆積するという問題を有し、ポ
リアクリル酸などの不飽和カルボン酸重合体は生分解性
に乏しいという問題がある。そこで、ビルダー作用と生
分解性とを有する水溶性重合体の開発が望まれている。
一方、環状ケテンアセタール類を含む単量体を重合して
なる、主鎖中にエステル結合を有する共重合体は加水分
解性を有するので、該共重合体をハウス園芸用フィル
ム、容器、緩衝材原料として用いることが提案されてい
る(特開平２ー２１４７１９)。2. Description of the Related Art Conventionally, in a detergent containing a surfactant as a main component, a builder is added as an auxiliary component of the surfactant to improve the washing performance. That is, polyvalent metal ions such as calcium ions and magnesium ions are usually present in water, and when combined with a surfactant, form a metal salt insoluble in water and reduce the detergency. The detergent builder is for preventing a surfactant generated by bonding with such a polyvalent metal ion from deteriorating in detergency. Further, in addition to such sequestering action, detergent builders are also required to have a dispersing action such as a re-contamination preventing action and an alkali buffering action. As detergent builders that meet these requirements, sodium and potassium carbonates, bicarbonates, phosphates,
Inorganic compounds such as polyphosphates, silicates and zeolites, and polymers of unsaturated carboxylic acids such as polyacrylic acid, polymaleic acid and polyitaconic acid are known. Among these builders, phosphates and polyphosphates have been widely used in terms of performance, safety and price, but since these phosphorus compounds cause eutrophication of rivers and lakes, At present, its use is restricted, and as an alternative, zeolite and unsaturated carboxylic acid polymer are provided.However, zeolite has a low solubility in water and has a problem that it is deposited on rivers and lakes, Unsaturated carboxylic acid polymers such as polyacrylic acid have a problem of poor biodegradability. Therefore, development of a water-soluble polymer having a builder action and biodegradability has been desired.
On the other hand, a copolymer having an ester bond in the main chain, which is obtained by polymerizing a monomer containing a cyclic ketene acetal, has hydrolyzability. It has been proposed to use it as a raw material (JP-A-2-214719).
【０００３】[0003]
【発明が解決しようとする課題】本発明は、ビルダー作
用と生分解性を有し、洗剤ビルダーとして有用な水溶性
重合体を得ることを課題とするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a water-soluble polymer having a builder action and biodegradability and useful as a detergent builder.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、前記目的
を達成するために鋭意研究を重ねた結果、新規な水溶性
共重合体がビルダー作用と生分解性をもつことを見いだ
し本発明を完成したのである。すなわち、本発明は、環
状ケテンアセタールと不飽和カルボン酸または不飽和カ
ルボン酸塩を必須構成単量体とすることを特徴とする水
溶性共重合体および該共重合体からなる洗剤ビルダーに
関するものである。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a novel water-soluble copolymer has a builder action and biodegradability. Was completed. That is, the present invention relates to a water-soluble copolymer characterized by comprising a cyclic ketene acetal and an unsaturated carboxylic acid or an unsaturated carboxylate as essential constituent monomers, and a detergent builder comprising the copolymer. is there.
【０００５】[0005]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明における環状ケテンアセタールは下記一般式(１)
で表される化合物である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The cyclic ketene acetal in the present invention has the following general formula (1)
It is a compound represented by these.
【０００６】[0006]
【化１】 Embedded image
【０００７】一般式(１)において、Ｒは二価の有機基を
表しており、一般式(１)で示される化合物の具体的なも
のとしては、2-メチレン-1,3-ジオキソラン、2-メチレ
ン-1,3-ジオサン、2-メチレン-1,3-ジオキセパンおよび
これらの誘導体などを挙げることができる。これらの化
合物のなかでも、2-メチレン-1,3-ジオキセパンが入手
の容易さ、取り扱い易さなどの面から、本発明にとり好
ましい化合物である。本発明における不飽和カルボン酸
としては、アクリル酸、メタクリル酸、マレイン酸、イ
タコン酸、フマル酸などが挙げらる。また水と反応して
容易にカルボキシル基を与える無水マレイン酸なども挙
げることができる。これらは単独で用いてもよく、二種
以上を組み合わせ用いてもよい。また、不飽和カルボン
酸塩としては、上記不飽和カルボン酸の水酸化ナトリウ
ム、水酸化カリウムなどのアルカリ塩、アルキルアミン
などのアミン塩、アンモニウム塩などが挙げられる。こ
れらのうち水酸化ナトリウム塩が本発明にとり好まし
い。これらの塩は単量体として重合に使用することも、
共重合された不飽和カルボン酸由来のカルボキシル基を
中和することにより、実質的に不飽和カルボン酸塩が共
重合された構造とすることができ、本発明にとり不飽和
カルボン酸を共重合し、ついで得られた共重合体のカル
ボキシル基の一部または全部を中和する方法が、本発明
の水溶性共重合体を得る方法として好ましい方法であ
る。In the general formula (1), R represents a divalent organic group. Specific examples of the compound represented by the general formula (1) include 2-methylene-1,3-dioxolan, 2 -Methylene-1,3-diosane, 2-methylene-1,3-dioxepane and derivatives thereof. Among these compounds, 2-methylene-1,3-dioxepane is a preferred compound for the present invention from the viewpoint of easy availability and easy handling. Examples of the unsaturated carboxylic acid in the present invention include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid and the like. Also, maleic anhydride which easily reacts with water to give a carboxyl group can be mentioned. These may be used alone or in combination of two or more. Examples of the unsaturated carboxylate include alkali salts of the above unsaturated carboxylic acids such as sodium hydroxide and potassium hydroxide, amine salts such as alkylamines, and ammonium salts. Of these, sodium hydroxide salts are preferred for the present invention. These salts can be used as monomers for polymerization,
By neutralizing the carboxyl group derived from the copolymerized unsaturated carboxylic acid, a structure in which the unsaturated carboxylic acid salt is substantially copolymerized can be obtained, and the unsaturated carboxylic acid is copolymerized according to the present invention. The method of neutralizing a part or all of the carboxyl groups of the obtained copolymer is a preferable method for obtaining the water-soluble copolymer of the present invention.
【０００８】本発明の共重合体は溶液重合法、懸濁重合
法、塊状重合法などにより前記単量体をラジカル重合す
ることにより得られる。ラジカル重合開始剤としては、
通常のラジカル重合開始剤を用いることができ、例え
ば、有機過酸化物、レドックス系開始剤、アゾ系開始剤
などを挙げることができる。本発明にとり好ましい方法
は、前記した環状ケテンアセタールと不飽和カルボン酸
を共重合し、ついで得られた共重合体のカルボキシル基
の一部または全部を中和して水溶性共重合体を得る方法
であり、共重合体中の全カルボキシル基の１−１００％
を中和するのが好ましく、より好ましくは１０−１００
％中和することであり、特に好ましいのは３０−１００
％の中和である。中和に際して用いられる塩基性化合物
としては、前記した塩を形成する、水酸化ナトリウム、
水酸化カリウムなどのアルカリ水酸化化合物、アルキル
アミンなどのアミン化合物、アンモニアなどが挙げら
れ、本発明には水酸化ナトリウムが好ましい。本発明の
共重合体はケテンアセタール由来のエステル結合含有単
位を含むものであり、その好ましい含有割合は５−９５
モル％であり、より好ましくは１０−９０モル％であ
り、特に好ましいのは１５−８５モル％である。本発明
の水溶性共重合体は、その重量平均分子量が５００ー２
０００００であることが好ましく、より好ましくは１０
００ー１０００００であり、特に好ましいのは２０００
−５００００のものである。以上の方法により、種々の
分子量、共重合体組成及び構造を有する本発明の水溶性
共重合体が得られる。[0008] The copolymer of the present invention can be obtained by radical polymerization of the above monomers by a solution polymerization method, a suspension polymerization method, a bulk polymerization method, or the like. As the radical polymerization initiator,
Conventional radical polymerization initiators can be used, and examples thereof include organic peroxides, redox initiators, and azo initiators. A preferred method for the present invention is a method of copolymerizing the above-described cyclic ketene acetal and an unsaturated carboxylic acid, and then neutralizing a part or all of the carboxyl groups of the obtained copolymer to obtain a water-soluble copolymer. And 1-100% of all carboxyl groups in the copolymer
Is preferably neutralized, more preferably 10-100
%, Particularly preferably 30-100%
% Neutralization. Examples of the basic compound used in the neutralization include sodium hydroxide,
Examples thereof include alkali hydroxide compounds such as potassium hydroxide, amine compounds such as alkylamines, and ammonia. In the present invention, sodium hydroxide is preferable. The copolymer of the present invention contains an ester bond-containing unit derived from ketene acetal, and the preferred content thereof is 5-95.
Mol%, more preferably 10-90 mol%, particularly preferably 15-85 mol%. The water-soluble copolymer of the present invention has a weight average molecular weight of 500-2.
00000, more preferably 10
00-100,000, particularly preferably 2000
-50,000. By the above method, the water-soluble copolymer of the present invention having various molecular weights, copolymer compositions and structures can be obtained.
【０００９】[0009]
【実施例】次に、実施例に基づき本発明をさらに詳細に
説明する。なお、カルシウムイオン捕捉能、クレイ分散
能、生分解率は、以下の方法により求めた。 ［カルシウムイオン捕捉能］ポリマー１０mgと０.００
１M塩化カルシウム／０.０８M塩化カリウム水溶液５０m
lを２５℃で混合し、溶液中のカルシウムイオン濃度を
イオンメーターにより測定した。カルシウムイオン捕捉
能は、ポリマー１gによって捕捉されたカルシウムイオ
ン量を炭酸カルシウム換算mgで表した。 ［クレイ分散能］ポリマー１０mgとグリシン緩衝液１０
０mlとクレイ(平均粒径０.０１８mm)１gを１００mlのメ
スシリンダーにいれ、２０回上下に振った。これを２０
時間静置させて上澄み液の５５０nmにおける吸光度を測
定し、その数値をクレイ分散能とした。 ［生分解率］ＪＩＳ規格Ｋ６９５０ー１９９４に規定さ
れている基礎培養基に試料を１００ppm、活性汚泥を３
０ppmの濃度になるように添加し、これを２５℃で２８
日間培養させた。生分解率は、この培養液中の全有機炭
素濃度を測定し、培養前後の全有機炭素濃度の減少率を
生分解性の値とした。Next, the present invention will be described in more detail with reference to examples. The calcium ion trapping ability, clay dispersing ability, and biodegradation rate were determined by the following methods. [Calcium ion scavenging ability] 10 mg of polymer and 0.00
50m 1M calcium chloride / 0.08M potassium chloride aqueous solution
were mixed at 25 ° C., and the calcium ion concentration in the solution was measured with an ion meter. The calcium ion trapping ability was represented by the amount of calcium ions trapped by 1 g of the polymer in terms of mg of calcium carbonate. [Clay dispersing ability] 10 mg of polymer and 10 glycine buffer
0 ml and 1 g of clay (average particle size 0.018 mm) were placed in a 100 ml measuring cylinder and shaken up and down 20 times. This is 20
After allowing to stand for a while, the absorbance of the supernatant at 550 nm was measured, and the value was used as the clay dispersing ability. [Biodegradation rate] 100 ppm of a sample and 3 parts of activated sludge in a basic culture medium specified in JIS K6950-1994.
It was added to a concentration of 0 ppm.
Cultured for days. The biodegradation rate was determined by measuring the total organic carbon concentration in the culture solution, and the rate of decrease in the total organic carbon concentration before and after cultivation was defined as the biodegradability value.
【００１０】（実施例１）2-メチレン-1,3-ジオキセパ
ン１gとアクリル酸２g、アゾビスイソブチロニトリル
０.０６g、イソプロピルアルコール６gを反応器に仕込
み、７５℃で３時間重合後、３２％水酸化ナトリウム水
溶液３.３gをくわえてカルボキシル基を中和させた。さ
らにメタノール４０g加えポリマーを沈殿させ、これを
濾別し、減圧乾燥させることで水溶性共重合体を得た。
得られた共重合体の赤外吸収スペクトルにおいて１７１
２cm-1にエステル結合のカルボニル基に由来するピーク
が観測された。またＧＰＣによる重量平均分子量(ポリ
アクリル酸換算)は１４１００であった。この共重合体
のカルシウム捕捉能は３６０mg/g、クレイ分散能は０.
５６、生分解率は１０％であった。(Example 1) 1 g of 2-methylene-1,3-dioxepane, 2 g of acrylic acid, 0.06 g of azobisisobutyronitrile and 6 g of isopropyl alcohol were charged into a reactor, and after polymerization at 75 ° C. for 3 hours, Carboxyl groups were neutralized by adding 3.3 g of a 32% aqueous sodium hydroxide solution. Further, 40 g of methanol was added to precipitate a polymer, which was separated by filtration and dried under reduced pressure to obtain a water-soluble copolymer.
The infrared absorption spectrum of the obtained copolymer was 171.
A peak derived from the carbonyl group of the ester bond was observed at 2 cm -1 . The weight average molecular weight (in terms of polyacrylic acid) by GPC was 14,100. This copolymer has a calcium capturing ability of 360 mg / g and a clay dispersing ability of 0.3 mg / g.
56, biodegradation rate was 10%.
【００１１】（実施例２）2-メチレン-1,3-ジオキセパ
ン１gと無水マレイン酸２g、アゾビスイソブチロニトリ
ル０.０６g、メチルエチルケトン６gを反応器に仕込
み、８０℃で３時間重合後、３２％水酸化ナトリウム水
溶液４.８gをくわえてカルボキシル基を中和させた。さ
らにメタノール４０g加えポリマーを沈殿させ、これを
濾別し、減圧乾燥させることで水溶性共重合体を得た。
得られた共重合体の赤外吸収スペクトルにおいて１７１
２cm-1にエステル結合のカルボニル基に由来するピーク
が観測された。またＧＰＣによる重量平均分子量(ポリ
アクリル酸換算)は４４００であった。この共重合体の
カルシウム捕捉能は２６０mg/g、クレイ分散能は０.８
５、生分解率は２０％であった。Example 2 1 g of 2-methylene-1,3-dioxepane, 2 g of maleic anhydride, 0.06 g of azobisisobutyronitrile and 6 g of methyl ethyl ketone were charged into a reactor, and after polymerization at 80 ° C. for 3 hours, The carboxyl group was neutralized by adding 4.8 g of a 32% aqueous sodium hydroxide solution. Further, 40 g of methanol was added to precipitate a polymer, which was separated by filtration and dried under reduced pressure to obtain a water-soluble copolymer.
The infrared absorption spectrum of the obtained copolymer was 171.
A peak derived from the carbonyl group of the ester bond was observed at 2 cm -1 . The weight average molecular weight (in terms of polyacrylic acid) by GPC was 4,400. This copolymer has a calcium capturing ability of 260 mg / g and a clay dispersing ability of 0.8.
5. The biodegradation rate was 20%.
【００１２】（実施例３）2-メチレン-1,3-ジオキセパ
ン２gとイタコン酸４g、アゾビスイソブチロニトリル
０.１２g、エタノール８gを反応器に仕込み、８０℃で
７時間重合後、３２％水酸化ナトリウム水溶液７.３gを
くわえてカルボキシル基を中和させた。さらにメタノー
ル８０gｇ加えポリマーを沈殿させ、これを濾別し、減
圧乾燥させることで水溶性共重合体を得た。得られた共
重合体の赤外吸収スペクトルにおいて１７１３cm-1にエ
ステル結合のカルボニル基に由来するピークが観測され
た。またＧＰＣによる重量平均分子量(ポリアクリル酸
換算)は２３００であった。この共重合体のカルシウム
捕捉能は２８０mg/g、クレイ分散能は１.２１、生分解
率は２２％であった。Example 3 2 g of 2-methylene-1,3-dioxepane, 4 g of itaconic acid, 0.12 g of azobisisobutyronitrile and 8 g of ethanol were charged into a reactor, and polymerized at 80 ° C. for 7 hours. The carboxyl group was neutralized by adding 7.3 g of an aqueous sodium hydroxide solution. Further, 80 g of methanol was added to precipitate a polymer, which was separated by filtration and dried under reduced pressure to obtain a water-soluble copolymer. In the infrared absorption spectrum of the obtained copolymer, a peak derived from a carbonyl group of an ester bond was observed at 1713 cm -1 . The weight average molecular weight (in terms of polyacrylic acid) by GPC was 2,300. The calcium scavenging ability of this copolymer was 280 mg / g, the clay dispersing ability was 1.21, and the biodegradation rate was 22%.
【００１３】（実施例４）反応器にトルエン４０g、無
水マレイン酸２６g、アゾビスイソブチロニトリル０.５
gを仕込み９０℃に加熱し、2-メチレン-1,3-ジオキセパ
ン１５gおよびアゾビスイソブチロニトリル２.０g／メ
チルエチルケトン５gを２時間かけて滴下した。滴下終
了後９０℃でさらに２時間重合後、３２％水酸化ナトリ
ウム水溶液４６gをくわえてカルボキシル基を中和させ
た。さらにメタノール加えポリマーを沈殿させ、これを
濾別し、減圧乾燥させることで水溶性共重合体を得た。
得られた共重合体の赤外吸収スペクトルにおいて１７２
５cm-1にエステル結合のカルボニル基に由来するピーク
が観測された。またＧＰＣによる重量平均分子量(ポリ
アクリル酸換算)は３７００であった。カルシウム捕捉
能は２４０mg/g、生分解率は１８％であった。Example 4 In a reactor, 40 g of toluene, 26 g of maleic anhydride, 0.5 azobisisobutyronitrile were used.
The mixture was heated to 90 ° C., and 15 g of 2-methylene-1,3-dioxepane and 2.0 g of azobisisobutyronitrile / 5 g of methyl ethyl ketone were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further polymerized at 90 ° C. for 2 hours. Then, 46 g of a 32% aqueous sodium hydroxide solution was added to neutralize the carboxyl groups. Further, methanol was added to precipitate a polymer, which was separated by filtration and dried under reduced pressure to obtain a water-soluble copolymer.
The infrared absorption spectrum of the obtained copolymer was 172.
A peak derived from the carbonyl group of the ester bond was observed at 5 cm -1 . The weight average molecular weight (in terms of polyacrylic acid) by GPC was 3,700. The calcium capturing ability was 240 mg / g, and the biodegradation rate was 18%.
【００１４】（比較例）ポリアクリル酸(重量平均分子
量８０００)のカルシウム捕捉能は、４１０mg/g、クレ
イ分散能は０.８２、生分解率は１％であった。Comparative Example Polyacrylic acid (weight average molecular weight: 8,000) had a calcium capturing ability of 410 mg / g, a clay dispersing ability of 0.82, and a biodegradation rate of 1%.
【００１５】[0015]
【発明の効果】本発明の共重合体は、洗剤ビルダーとし
て実績のあるポリアクリル酸と同等のビルダー機能を有
するうえに、生分解性をも有するという優れた性能を発
揮するもので、洗剤ビルダーとして広く採用されうるも
のである。Industrial Applicability The copolymer of the present invention has the same builder function as polyacrylic acid, which has been proven as a detergent builder, and also exhibits excellent performance of having biodegradability. It can be widely adopted as
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4H003 EB30 EB32 EB35 FA03 FA04 FA07 4J029 AA07 AB01 AC02 AD01 AE18 BF30 GA05 GA12 GA13 GA14 GA17 GA42 GA43 HB01 JF032 JF042 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H003 EB30 EB32 EB35 FA03 FA04 FA07 4J029 AA07 AB01 AC02 AD01 AE18 BF30 GA05 GA12 GA13 GA14 GA17 GA42 GA43 HB01 JF032 JF042
Claims (2)
酸または不飽和カルボン酸塩を必須構成単量体とするこ
とを特徴とする水溶性共重合体。1. A water-soluble copolymer comprising a cyclic ketene acetal and an unsaturated carboxylic acid or an unsaturated carboxylate as essential constituent monomers.
洗剤ビルダー。2. A detergent builder comprising the water-soluble copolymer according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10225481A JP2000038595A (en) | 1998-07-24 | 1998-07-24 | Water-soluble copolymer and detergent builder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10225481A JP2000038595A (en) | 1998-07-24 | 1998-07-24 | Water-soluble copolymer and detergent builder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000038595A true JP2000038595A (en) | 2000-02-08 |
Family
ID=16830010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10225481A Pending JP2000038595A (en) | 1998-07-24 | 1998-07-24 | Water-soluble copolymer and detergent builder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000038595A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008024730A (en) * | 2006-07-18 | 2008-02-07 | National Institute Of Advanced Industrial & Technology | Biodegradable alternating copolymer and cleaning builder using the same |
| WO2009127600A1 (en) * | 2008-04-14 | 2009-10-22 | Philipps-Universität Marburg | Hydrolytically decomposable ionic copolymers |
| CN105566554A (en) * | 2014-10-17 | 2016-05-11 | 上海东升新材料有限公司 | Detergent assistant with fumaric acid serving as main synthesis raw material and preparation method of detergent assistant |
| CN110746525A (en) * | 2019-10-25 | 2020-02-04 | 华南理工大学 | Easily-degradable sterilization type washing assistant and preparation method and application thereof |
| WO2023008367A1 (en) | 2021-07-27 | 2023-02-02 | 株式会社日本触媒 | Ester bond-containing polycarboxylic acid (salt) and method for producing same |
| WO2025032252A1 (en) | 2023-08-09 | 2025-02-13 | Snf Sa | Precipitation polymerization process for obtaining degradable polymers |
| WO2025032253A1 (en) | 2023-08-09 | 2025-02-13 | Snf Sa | Polymerization method for obtaining polymers with improved degradability |
| WO2025083341A1 (en) | 2023-10-20 | 2025-04-24 | Coatex - Balmefrezol, Ludovic | Preparation of an ester copolymer |
| WO2025083340A1 (en) | 2023-10-20 | 2025-04-24 | Coatex | Thioester copolymer |
-
1998
- 1998-07-24 JP JP10225481A patent/JP2000038595A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008024730A (en) * | 2006-07-18 | 2008-02-07 | National Institute Of Advanced Industrial & Technology | Biodegradable alternating copolymer and cleaning builder using the same |
| WO2009127600A1 (en) * | 2008-04-14 | 2009-10-22 | Philipps-Universität Marburg | Hydrolytically decomposable ionic copolymers |
| CN105566554A (en) * | 2014-10-17 | 2016-05-11 | 上海东升新材料有限公司 | Detergent assistant with fumaric acid serving as main synthesis raw material and preparation method of detergent assistant |
| CN110746525A (en) * | 2019-10-25 | 2020-02-04 | 华南理工大学 | Easily-degradable sterilization type washing assistant and preparation method and application thereof |
| WO2023008367A1 (en) | 2021-07-27 | 2023-02-02 | 株式会社日本触媒 | Ester bond-containing polycarboxylic acid (salt) and method for producing same |
| WO2025032252A1 (en) | 2023-08-09 | 2025-02-13 | Snf Sa | Precipitation polymerization process for obtaining degradable polymers |
| WO2025032253A1 (en) | 2023-08-09 | 2025-02-13 | Snf Sa | Polymerization method for obtaining polymers with improved degradability |
| FR3152026A1 (en) * | 2023-08-09 | 2025-02-14 | Snf Sa | POLYMERIZATION PROCESS FOR OBTAINING POLYMERS WITH IMPROVED DEGRADABILITY |
| FR3152025A1 (en) * | 2023-08-09 | 2025-02-14 | Snf Sa | PRECIPITATION POLYMERIZATION PROCESS FOR OBTAINING DEGRADABLE POLYMERS |
| WO2025083341A1 (en) | 2023-10-20 | 2025-04-24 | Coatex - Balmefrezol, Ludovic | Preparation of an ester copolymer |
| WO2025083340A1 (en) | 2023-10-20 | 2025-04-24 | Coatex | Thioester copolymer |
| FR3154399A1 (en) * | 2023-10-20 | 2025-04-25 | Coatex | Preparation of an ester copolymer |
| FR3154400A1 (en) * | 2023-10-20 | 2025-04-25 | Coatex | Thioester copolymer |
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