JP2017148780A - Thickener, slurry for exhaust gas purification catalyst and manufacturing method therefor and internal combustion engine - Google Patents
Thickener, slurry for exhaust gas purification catalyst and manufacturing method therefor and internal combustion engine Download PDFInfo
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- JP2017148780A JP2017148780A JP2016035963A JP2016035963A JP2017148780A JP 2017148780 A JP2017148780 A JP 2017148780A JP 2016035963 A JP2016035963 A JP 2016035963A JP 2016035963 A JP2016035963 A JP 2016035963A JP 2017148780 A JP2017148780 A JP 2017148780A
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- slurry
- exhaust gas
- acid
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- meth
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000002562 thickening agent Substances 0.000 title claims abstract description 54
- 238000000746 purification Methods 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000002485 combustion reaction Methods 0.000 title claims description 9
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Images
Abstract
Description
本発明は、増粘剤、排ガス浄化触媒用スラリー、排ガス浄化触媒の製造方法及び内燃機関に関する。 The present invention relates to a thickener, a slurry for exhaust gas purification catalyst, a method for producing an exhaust gas purification catalyst, and an internal combustion engine.
従来、排ガス浄化触媒の調製において、排ガス浄化触媒用スラリーの垂れを防止するために、固形分濃度を高くすることにより粘度を高くしてから塗布する方法が採用されている。なお、排ガス浄化触媒用スラリーの粘度を下げるための減粘剤は知られているが(たとえば特許文献1)、この粘度を上げるための増粘剤は知られていない。 Conventionally, in the preparation of an exhaust gas purification catalyst, in order to prevent dripping of the slurry for exhaust gas purification catalyst, a method of applying after increasing the viscosity by increasing the solid content concentration has been adopted. In addition, although the thinning agent for lowering | hanging the viscosity of the slurry for exhaust gas purification catalysts is known (for example, patent document 1), the thickening agent for raising this viscosity is not known.
排ガス浄化触媒用スラリーの垂れを防止するために、固形分濃度を高くすることにより粘度を高くしてから塗布する場合、固形分濃度が高いために排ガス触媒層を薄くすることができないという問題がある。
本発明は、排ガス浄化触媒用スラリーの固形分濃度を高くしなくても粘度を高くすることができる増粘効果に優れた増粘剤を提供することである。
In order to prevent dripping of the slurry for exhaust gas purification catalyst, when applying after increasing the viscosity by increasing the solid content concentration, there is a problem that the exhaust gas catalyst layer cannot be thinned due to the high solid content concentration. is there.
This invention is providing the thickener excellent in the thickening effect which can make a viscosity high, without making solid content concentration of the slurry for exhaust gas purification catalysts high.
本発明の増粘剤の特徴は、貴金属を担持した耐熱性無機酸化物及び分散媒を含む排ガス浄化触媒用スラリーの粘度を上昇させるための増粘剤であって、
(メタ)アクリル酸(A)単位と(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位とから構成される共重合体(X)を含有してなり、
(メタ)アクリル酸(A)単位及び(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位のモル数に基づいて、(メタ)アクリル酸(A)単位の含有量が80〜97モル%、(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位の含有量が3〜20モル%であり、共重合体(X)の重量平均分子量が1万〜3万である点を要旨とする。
The thickener of the present invention is characterized in that it is a thickener for increasing the viscosity of a slurry for exhaust gas purification catalyst containing a heat-resistant inorganic oxide supporting a noble metal and a dispersion medium,
Containing a copolymer (X) composed of (meth) acrylic acid (A) units and (meth) acrylic acid alkoxypolyoxyalkylene ester (B) units;
Based on the number of moles of the (meth) acrylic acid (A) unit and the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit, the content of the (meth) acrylic acid (A) unit is 80 to 97 mol%, The gist is that the content of the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit is 3 to 20 mol%, and the weight average molecular weight of the copolymer (X) is 10,000 to 30,000.
本発明の排ガス浄化触媒用スラリーの特徴は、上記の増粘剤、貴金属を担持した耐熱性無機酸化物及び分散媒を含んでなる点を要旨とする。 A feature of the slurry for exhaust gas purification catalyst of the present invention is that it comprises the above thickener, a heat-resistant inorganic oxide carrying a noble metal, and a dispersion medium.
本発明の排ガス浄化触媒の製造方法の特徴は、上記の増粘剤、貴金属を担持した耐熱性無機酸化物及び分散媒を均一混合分散してスラリーを得るスラリー化工程(1)、
基材に、スラリーを塗布して塗布基材を得る塗布工程(2)、並びに
塗布基材を乾燥し、焼成して排気ガス浄化触媒を得る乾燥焼成工程(3)を含む点を要旨とする。
A feature of the method for producing an exhaust gas purifying catalyst of the present invention is a slurrying step (1) for obtaining a slurry by uniformly mixing and dispersing the thickener, a heat-resistant inorganic oxide supporting a noble metal, and a dispersion medium,
The gist includes a coating step (2) for applying a slurry to a substrate to obtain a coated substrate, and a drying and firing step (3) for drying and firing the coated substrate to obtain an exhaust gas purification catalyst. .
本発明の内燃機関の特徴は、上記の製造方法で製造される排ガス浄化用触媒を搭載する点を要旨とする。 The feature of the internal combustion engine of the present invention is that the exhaust gas purifying catalyst manufactured by the above manufacturing method is mounted.
本発明の増粘剤は、貴金属を担持した耐熱性無機酸化物及び分散媒を含む排ガス浄化触媒用スラリーの粘度を効果的に上昇させることができる(すなわち、増粘効果に優れている)。したがって、本発明の増粘剤を用いると、排ガス浄化触媒用スラリーの固形分濃度を高くしなくても粘度を高くでき、排ガス触媒層を薄くすることができる。 The thickener of the present invention can effectively increase the viscosity of a slurry for an exhaust gas purification catalyst containing a heat-resistant inorganic oxide supporting a noble metal and a dispersion medium (that is, excellent in the thickening effect). Therefore, when the thickener of the present invention is used, the viscosity can be increased without increasing the solid content concentration of the slurry for exhaust gas purification catalyst, and the exhaust gas catalyst layer can be made thinner.
本発明の排ガス浄化触媒用スラリーは、上記の増粘剤を用いているため、粘度を効果的に上昇でき、固形分濃度を高くしなくても、排ガス触媒層を薄くすることができる。 Since the slurry for exhaust gas purification catalyst of the present invention uses the above thickener, the viscosity can be effectively increased and the exhaust gas catalyst layer can be made thin without increasing the solid content concentration.
本発明の排ガス浄化触媒の製造方法は、上記の増粘剤を用いているため、粘度を効果的に上昇でき、スラリーの固形分濃度を高くしなくても、排ガス触媒層を薄くすることができる。 Since the manufacturing method of the exhaust gas purification catalyst of the present invention uses the above thickener, the viscosity can be effectively increased, and the exhaust gas catalyst layer can be made thin without increasing the solid content concentration of the slurry. it can.
本発明の内燃機関は、上記の増粘剤を用いているため、排ガス触媒層を薄くすることができる。 Since the internal combustion engine of the present invention uses the above thickener, the exhaust gas catalyst layer can be made thin.
<増粘剤>
(メタ)アクリル酸(A)単位としては、アクリル酸単位及びメタクリル酸単位が含まれる。
<Thickener>
The (meth) acrylic acid (A) unit includes an acrylic acid unit and a methacrylic acid unit.
(メタ)アクリル酸(A)単位の含有量(モル%)は、(メタ)アクリル酸(A)単位及び(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位のモル数に基づいて、80〜97が好ましく、さらに好ましくは82〜96、特に好ましくは84〜95である。この範囲内であると、増粘効果がさらに良好となる。 The content (mol%) of the (meth) acrylic acid (A) unit is 80 based on the number of moles of the (meth) acrylic acid (A) unit and the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit. -97 are preferable, More preferably, it is 82-96, Most preferably, it is 84-95. Within this range, the thickening effect is further improved.
(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位としては、アクリル酸アルコキシポリオキシアルキレンエステル単位及びメタクリル酸アルコキシポリオキシアルキレンエステル単位が含まれる。 The (meth) acrylic acid alkoxy polyoxyalkylene ester (B) unit includes an acrylic acid alkoxy polyoxyalkylene ester unit and a methacrylic acid alkoxy polyoxyalkylene ester unit.
オキシアルキレンとしては、炭素数2〜4のオキシアルキレン(オキシエチレン、オキシプロピレン及びオキシブチレン)が含まれる。これらのうち、オキシエチレンが好ましい。 Examples of oxyalkylene include oxyalkylene having 2 to 4 carbon atoms (oxyethylene, oxypropylene and oxybutylene). Of these, oxyethylene is preferred.
ポリオキシアルキレンは、1種のオキシアルキレンから構成されてもよく、2種以上のオキシアルキレンから構成されてもよい。2種以上のオキシアルキレンから構成される場合、結合様式はブロック、ランダム及びこれの混合のいずれでもよい。これらのうち、オキシエチレンから構成されるか、オキシエチレンを含む2種以上のオキシアルキレンから構成されることが好ましく、さらに好ましくはオキシエチレンから構成されることである。すなわち、(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位としては、(メタ)アクリル酸アルコキシポリオキシエチレンエステル(B1)単位が好ましい。 The polyoxyalkylene may be composed of one kind of oxyalkylene or may be composed of two or more kinds of oxyalkylene. When composed of two or more oxyalkylenes, the bonding mode may be block, random, or a mixture thereof. Among these, it is preferable that it is comprised from oxyethylene or it is comprised from 2 or more types of oxyalkylene containing oxyethylene, More preferably, it is comprised from oxyethylene. That is, the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit is preferably a (meth) acrylic acid alkoxypolyoxyethylene ester (B1) unit.
ポリオキシアルキレンの重合度としては、増粘効果の観点から、1〜100が好ましく、さらに好ましくは4〜60、特に好ましくは10〜40である。 The degree of polymerization of the polyoxyalkylene is preferably 1 to 100, more preferably 4 to 60, and particularly preferably 10 to 40 from the viewpoint of the thickening effect.
アルコキシポリオキシアルキレン中のアルコキシ基としては、炭素数1〜30の直鎖アルキルオキシ基及び炭素数3〜30の分岐鎖アルキルオキシ基等が使用できる。 As an alkoxy group in alkoxy polyoxyalkylene, a C1-C30 linear alkyloxy group, a C3-C30 branched alkyloxy group, etc. can be used.
直鎖アルキルアルコキシ基としては、メトキシ、エトキシ、プロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ、ヘプチルオキシ、オクチルオキシ、ノニルオキシ、デシルオキシ、ウンデシルオキシ、ドデシルオキシ、トリデシルオキシ、テトラデシルオキシ、ペンタデシルオキシ、ヘキサデシルオキシ、ヘプタデシルオキシ、オクタデシルオキシ、ノナデシルオキシ、イコシルオキシ、ヘニコシルオキシ、ドコシルオキシ、トリコシルオキシ、テトラコシルオキシ、ヘプタコシルオキシ、ヘキサコシルオキシ、ヘプタコシルオキシ、オクタコシルオキシ、ノナコシルオキシ及びトリアコンシルオキシ等が挙げられる。 Linear alkyl alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy , Hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, icosyloxy, henicosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, heptacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy And triaconyloxy and the like.
分岐鎖アルキルアルコキシ基としては、イソプロピルオキシ、イソブチルオキシ、t−ブチルオキシ、イソペンチルオキシ、ネオペンチルオキシ、イソヘキシルオキシ、2−エチルヘキシルオキシ、イソトリデシルオキシ、イソオクタデシルオキシ及びイソトリアコンシルオキシ等が挙げられる。 Examples of branched alkylalkoxy groups include isopropyloxy, isobutyloxy, t-butyloxy, isopentyloxy, neopentyloxy, isohexyloxy, 2-ethylhexyloxy, isotridecyloxy, isooctadecyloxy, and isotriaconcyloxy Is mentioned.
これらのアルコキシ基のうち、増粘効果の観点から、直鎖アルキルオキシ基が好ましく、さらに好ましくは炭素数1〜18の直鎖アルキルオキシ基、特に好ましくはメトキシ、エトキシ及びオクタデシルオキシである。 Of these alkoxy groups, a linear alkyloxy group is preferable from the viewpoint of thickening effect, more preferably a linear alkyloxy group having 1 to 18 carbon atoms, and particularly preferably methoxy, ethoxy and octadecyloxy.
(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位の含有量(モル%)は、(メタ)アクリル酸(A)単位及び(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位のモル数に基づいて、3〜20が好ましく、さらに好ましくは4〜18、特に好ましくは5〜16である。この範囲内であると、増粘効果がさらに良好となる。 The content (mol%) of the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit is the number of moles of the (meth) acrylic acid (A) unit and the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit. Is preferably 3 to 20, more preferably 4 to 18, and particularly preferably 5 to 16. Within this range, the thickening effect is further improved.
共重合体(X)は、(メタ)アクリル酸(A)及び(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)以外に、他のエチレン性不飽和単量体(C)を構成単量体として含むことができる。 The copolymer (X) is composed of other ethylenically unsaturated monomers (C) in addition to (meth) acrylic acid (A) and (meth) acrylic acid alkoxypolyoxyalkylene ester (B). Can be included as
他のエチレン性不飽和単量体(C)としては、(メタ)アクリル酸(A)及び(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)と共重合できれば特に制限はなく、エチレン性不飽和カルボン酸、エチレン性不飽和カルボン酸塩、オレフィン、エチレン性不飽和ニトリル及びエチレン性不飽和アミド等が挙げられる。 The other ethylenically unsaturated monomer (C) is not particularly limited as long as it can be copolymerized with (meth) acrylic acid (A) and (meth) acrylic acid alkoxypolyoxyalkylene ester (B). Examples thereof include carboxylic acid, ethylenically unsaturated carboxylate, olefin, ethylenically unsaturated nitrile and ethylenically unsaturated amide.
エチレン性不飽和カルボン酸としては、エチレン性不飽和モノカルボン酸及びエチレン性不飽和ジカルボン酸が含まれる。 Examples of the ethylenically unsaturated carboxylic acid include ethylenically unsaturated monocarboxylic acid and ethylenically unsaturated dicarboxylic acid.
エチレン性不飽和モノカルボン酸としては、脂肪族モノカルボン酸、脂環式モノカルボン酸及び芳香族モノカルボン酸が含まれる。 Examples of ethylenically unsaturated monocarboxylic acids include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids.
脂肪族モノカルボン酸としては、クロトン酸、3−ブテン酸、2−ペンテン酸、3−ペンテン酸、4−ペンテン酸、3−メチル−2−ブテン酸、3−メチル−3−ブテン酸、2−メチル−3−ブテン酸、2−メチル−2−ブテン酸、2−エチル−2−プロペン酸、2−ヘキセン酸、4−メチル−2−ペンテン酸、2−メチル−2−ペンテン酸、2−ヘプテン酸、4,4−ジメチル−2−ペンテン酸、2−オクテン酸、3−メチル−2−ヘプテン酸、2−ノネン酸、3−メチル−2−オクテン酸、2−デケン酸及び2−ヒドロキシプロペン酸等が挙げられる。 Aliphatic monocarboxylic acids include crotonic acid, 3-butenoic acid, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, 3-methyl-2-butenoic acid, 3-methyl-3-butenoic acid, 2 -Methyl-3-butenoic acid, 2-methyl-2-butenoic acid, 2-ethyl-2-propenoic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 2 -Heptenoic acid, 4,4-dimethyl-2-pentenoic acid, 2-octenoic acid, 3-methyl-2-heptenoic acid, 2-nonenoic acid, 3-methyl-2-octenoic acid, 2-decenoic acid and 2- And hydroxypropenoic acid.
脂環式モノカルボン酸としては、1−シクロペンテンカルボン酸、3−シクロペンテンカルボン酸、4−シクロペンテンカルボン酸、1−シクロヘキセンカルボン酸、3−シクロヘキセンカルボン酸、4−シクロヘキセンカルボン酸、1−シクロヘプテンカルボン酸、3−シクロヘプテンカルボン酸、4−シクロヘプテンカルボン酸、5−シクロヘプテンカルボン酸、1−シクロオクテンカルボン酸、3−シクロオクテンカルボン酸、4−シクロオクテンカルボン酸、5−シクロオクテンカルボン酸、1−シクロノネンカルボン酸、3−シクロノネンカルボン酸、4−シクロノネンカルボン酸、5−シクロノネンカルボン酸、1−シクロデケンカルボン酸、3−シクロデケンカルボン酸、4−シクロデケンカルボン酸及び5−シクロデケンカルボン酸等が挙げられる。 Examples of the alicyclic monocarboxylic acid include 1-cyclopentenecarboxylic acid, 3-cyclopentenecarboxylic acid, 4-cyclopentenecarboxylic acid, 1-cyclohexenecarboxylic acid, 3-cyclohexenecarboxylic acid, 4-cyclohexenecarboxylic acid, and 1-cycloheptene. Carboxylic acid, 3-cycloheptenecarboxylic acid, 4-cycloheptenecarboxylic acid, 5-cycloheptenecarboxylic acid, 1-cyclooctenecarboxylic acid, 3-cyclooctenecarboxylic acid, 4-cyclooctenecarboxylic acid, 5- Cyclooctenecarboxylic acid, 1-cyclononenecarboxylic acid, 3-cyclononenecarboxylic acid, 4-cyclononenecarboxylic acid, 5-cyclononenecarboxylic acid, 1-cyclodecenecarboxylic acid, 3-cyclodecenecarboxylic acid, 4-cyclo Dekencarboxylic acid and 5-cyclodekaenka Bonn acid and the like.
芳香族モノカルボン酸としては、o−スチレンカルボン酸、p−スチレンカルボン酸、桂皮酸、アトロパ酸、5−ビニル−1−ナフタレンカルボン酸、4−ビニル−1−ナフタレンカルボン酸及び4−ビニル−1−アントラキノンカルボン酸等が挙げられる。 As aromatic monocarboxylic acids, o-styrene carboxylic acid, p-styrene carboxylic acid, cinnamic acid, atropic acid, 5-vinyl-1-naphthalene carboxylic acid, 4-vinyl-1-naphthalene carboxylic acid and 4-vinyl- Examples include 1-anthraquinone carboxylic acid.
エチレン性不飽和ジカルボン酸としては、脂肪族ジカルボン酸、脂環式ジカルボン酸、芳香族ジカルボン酸及びこれらの分子内酸無水物等が挙げられる。 Examples of the ethylenically unsaturated dicarboxylic acid include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, and intramolecular acid anhydrides thereof.
脂肪族ジカルボン酸としては、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸、ブテン二酸、2−ペンテン二酸、3−ペンテン酸、4−ペンテン酸、2−メチル−2−ブテン二酸、2−エチル−2−プロペン酸、2−ヘキセン二酸、2−ヘプテン二酸、2−オクテン酸、3−メチル−2−ヘプテン二酸、2−ノネン二酸、2−デケン二酸及び2−ヒドロキシプテンロ二酸等が挙げられる。 Examples of aliphatic dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, butenedioic acid, 2-pentenedioic acid, 3-pentenoic acid, 4-pentenoic acid, 2-methyl-2-butene Acid, 2-ethyl-2-propenoic acid, 2-hexenedioic acid, 2-heptenedioic acid, 2-octenoic acid, 3-methyl-2-heptenedioic acid, 2-nonenedioic acid, 2-decenedioic acid and Examples include 2-hydroxyptenelodioic acid.
脂環式ジカルボン酸としては、1,2−シクロペンテンジカルボン酸、1,3−シクロペンテンジカルボン酸、1,4−シクロペンテンジカルボン酸、1,2−シクロヘキセンジカルボン酸、1,3−シクロヘキセンジカルボン酸、1,4−シクロヘキセンジカルボン酸、1,2−シクロヘプテンジカルボン酸、1,3−シクロヘプテンジカルボン酸、1,4−シクロヘプテンジカルボン酸、1,5−シクロヘプテンジカルボン酸、1,2−シクロオクテンジカルボン酸、1,3−シクロオクテンジカルボン酸、1,4−シクロオクテンジカルボン酸、1,5−シクロオクテンジカルボン酸、1,2−シクロノネンジカルボン酸、1,3−シクロノネンジカルボン酸、1,4−シクロノネンジカルボン酸、1,5−シクロノネンジカルボン酸、1,2−シクロデケンジカルボン酸、1,3−シクロデケンジカルボン酸、1,4−シクロデケンジカルボン酸及び1,5−シクロデケンジカルボン酸等が挙げられる。 Examples of the alicyclic dicarboxylic acid include 1,2-cyclopentene dicarboxylic acid, 1,3-cyclopentene dicarboxylic acid, 1,4-cyclopentene dicarboxylic acid, 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid, 4-cyclohexene dicarboxylic acid, 1,2-cycloheptene dicarboxylic acid, 1,3-cycloheptene dicarboxylic acid, 1,4-cycloheptene dicarboxylic acid, 1,5-cycloheptene dicarboxylic acid, 1,2- Cyclooctene dicarboxylic acid, 1,3-cyclooctene dicarboxylic acid, 1,4-cyclooctene dicarboxylic acid, 1,5-cyclooctene dicarboxylic acid, 1,2-cyclononene dicarboxylic acid, 1,3-cyclononene dicarboxylic acid, 1,4-cyclononene dicarboxylic acid, 1,5-cyclononene dicarboxylic acid, 1,2-cyclodecenedicarboxylic acid, 1,3-cyclodecenedicarboxylic acid, 1,4-cyclodecenedicarboxylic acid, 1,5-cyclodecenedicarboxylic acid and the like can be mentioned.
芳香族ジカルボン酸としては、o,p−スチレンジカルボン酸、o,p−スチレンジカルボン酸、4−ビニル−1,2−ナフタレンジカルボン酸及び4−ビニル−1,3−アントラキノンジカルボン酸等が挙げられる。 Examples of the aromatic dicarboxylic acid include o, p-styrene dicarboxylic acid, o, p-styrene dicarboxylic acid, 4-vinyl-1,2-naphthalenedicarboxylic acid and 4-vinyl-1,3-anthraquinone dicarboxylic acid. .
不飽和ジカルボン酸の分子内酸無水物としては、無水マレイン酸、無水イタコン酸及び無水シトラコン酸等が挙げられる。 Examples of intramolecular acid anhydrides of unsaturated dicarboxylic acids include maleic anhydride, itaconic anhydride, and citraconic anhydride.
エチレン性不飽和カルボン酸塩としては、エチレン性不飽和カルボン酸のアルカリ金属塩、アルカリ土類金属塩、アミン塩、アンモニウム塩及び/又は第4級有機アンモニウム塩が含まれる。
なお、エチレン性不飽和カルボン酸は、エチレン性不飽和カルボン酸で説明したエチレン性不飽和モノカルボン酸及びエチレン性不飽和ジカルボン酸が含まれる。
Examples of the ethylenically unsaturated carboxylate include alkali metal salts, alkaline earth metal salts, amine salts, ammonium salts and / or quaternary organic ammonium salts of ethylenically unsaturated carboxylic acids.
The ethylenically unsaturated carboxylic acid includes the ethylenically unsaturated monocarboxylic acid and the ethylenically unsaturated dicarboxylic acid described for the ethylenically unsaturated carboxylic acid.
アルカリ金属塩としては、リチウム、カリウム又はナトリウム等の塩が挙げられる。
アルカリ土類金属塩としては、カルシウム又はマグネシウム等の塩が挙げられる。
アミン塩としては、炭素数2〜6の脂肪族アミン、炭素数3〜6の脂環式アミン又は炭素数6〜8の芳香族アミン等の塩が挙げられる。
Examples of the alkali metal salt include lithium, potassium and sodium salts.
Examples of the alkaline earth metal salt include salts such as calcium or magnesium.
As an amine salt, salts, such as a C2-C6 aliphatic amine, a C3-C6 alicyclic amine, or a C6-C8 aromatic amine, are mentioned.
脂肪族アミンとしては、エチルアミン、ジエチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、2−アミノ−2−メチルプロパノール、ジメチルエタノールアミン、ジエチルエタノールアミン及びエチレンジアミン等が挙げられる。 Examples of the aliphatic amine include ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, dimethylethanolamine, diethylethanolamine, and ethylenediamine.
脂環式アミンとしては、シクロプロピルアミン、シクロブチルアミン、シクロペンチルアミン及びシクロへキシルアミン等が挙げられる。 Examples of alicyclic amines include cyclopropylamine, cyclobutylamine, cyclopentylamine, and cyclohexylamine.
芳香族アミンとしては、アニリン、ピリジン、ピペリジン、ベンジルアミン及びフェニレンジアミン等が挙げられる。 Examples of the aromatic amine include aniline, pyridine, piperidine, benzylamine, and phenylenediamine.
第4級有機アンモニウム塩としては、炭素数4〜8の有機アンモニウム塩等が使用でき、テトラメチルアンモニウム塩、テトラエチルアンモニウム塩、トリメチルエチルアンモニウム塩、N−メチルピリジニウム塩及びN−メチルイミダゾリウム塩等が挙げられる。 As the quaternary organic ammonium salt, an organic ammonium salt having 4 to 8 carbon atoms can be used, such as tetramethylammonium salt, tetraethylammonium salt, trimethylethylammonium salt, N-methylpyridinium salt and N-methylimidazolium salt. Is mentioned.
オレフィンとしては、炭素数2〜20のα−オレフィン(エチレン、プロピレン、ブチレン、へキシレン、オクチレン、ウンデシレン、テトラデシレン及びノナデシレン等)、ジイソブチレン、ブタジエン、ピペリレン、クロロプレン、ピネン、リモネン、インデン、シクロペンタジエン、ビシクロペンタジエン及びエチリデンノルボルネン等が挙げられる。 Examples of the olefin include α-olefins having 2 to 20 carbon atoms (ethylene, propylene, butylene, hexylene, octylene, undecylene, tetradecylene, and nonadecylene), diisobutylene, butadiene, piperylene, chloroprene, pinene, limonene, indene, and cyclopentadiene. , Bicyclopentadiene, ethylidene norbornene and the like.
エチレン性不飽和ニトリルとしては、(メタ)アクリロニトリル、シアノプロペン及びシアノペンテン等が挙げられる。 Examples of the ethylenically unsaturated nitrile include (meth) acrylonitrile, cyanopropene and cyanopentene.
エチレン性不飽和アミドとしては、(メタ)アクリルアミド、N−メチル(メタ)アクリルアミド、N−2−ヒドロキシエチル(メタ)アクリルアミド、N−(2−アミノエチル)(メタ)アクリルアミド及びN−(2−ジメチルアミノエチル)(メタ)アクリルアミド等が挙げられる。 Examples of the ethylenically unsaturated amide include (meth) acrylamide, N-methyl (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N- (2-aminoethyl) (meth) acrylamide and N- (2- And dimethylaminoethyl) (meth) acrylamide.
他のエチレン性不飽和単量体(C)単位を含む場合、他のエチレン性不飽和単量体(C)単位の含有量(モル%)は、(メタ)アクリル酸(A)単位及び(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位のモル数に基づいて、0.1〜20が好ましく、さらに好ましくは0.5〜15、特に好ましくは1〜10であるが、他のエチレン性不飽和単量体(C)単位を含まないことが最も好ましい。 When other ethylenically unsaturated monomer (C) units are included, the content (mol%) of the other ethylenically unsaturated monomer (C) units is (meth) acrylic acid (A) units and ( Based on the number of moles of the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit, 0.1-20 are preferable, more preferably 0.5-15, and particularly preferably 1-10, but other ethylene. Most preferably, it does not contain a unit of the unsaturated monomer (C).
共重合体(X)の重量平均分子量(Mw)は、増粘効果の観点から、1万〜3万が好ましく、さらに好ましくは1.1万〜2.8万、特に好ましくは1.2万〜2.6万である。 The weight average molecular weight (Mw) of the copolymer (X) is preferably 10,000 to 30,000, more preferably 11,000 to 28,000, and particularly preferably 12,000 from the viewpoint of the thickening effect. ~ 26,000.
なお、重量平均分子量(Mw)は、分子量既知の(ポリ)エチレングリコールを標準物質として、ゲルパーミエーションクロマトグラフィー(GPC)法で測定される(たとえば、カラム温度40℃、溶離液 メタノール:イオン交換水:酢酸ナトリウム=800:1200:15(重量比)、流速0.8ml/分、試料濃度:0.4重量%溶離液溶液。)。 The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) using (poly) ethylene glycol of known molecular weight as a standard substance (for example, column temperature 40 ° C., eluent methanol: ion exchange) Water: sodium acetate = 800: 1200: 15 (weight ratio), flow rate 0.8 ml / min, sample concentration: 0.4 wt% eluent solution.).
共重合体(X)は、通常のビニルモノマーの重合方法を用いて得ることができ、重合方法としては懸濁重合、塊状重合及び溶液重合等が適用でき、生産性の観点等から、溶液重合が好ましい。 The copolymer (X) can be obtained using a usual vinyl monomer polymerization method, and suspension polymerization, bulk polymerization, solution polymerization, etc. can be applied as the polymerization method. From the viewpoint of productivity, solution polymerization is possible. Is preferred.
重合には、重合触媒を使用することができる。重合触媒としては、通常の重合触媒等が用いられ、アゾ化合物、過硫酸塩、無機過酸化物、レドックス触媒及び有機過酸化物が含まれる。アゾ化合物としては、2,2’−アゾビスイソブチロニトリル、4,4’−アゾビス−4−シアノバレリン酸、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル、2,2’−アゾビス(2−メチルブチロニトリル)、1,1’−アゾビス(シクロヘキサン−1−アルボニトリル)、2,2’−アゾビス(2,4,4−トリメチルペンタン)、ジメチル2,2’−アゾビス(2−メチルプロピオネート)、2,2’−アゾビス[2−(ヒドロキシメチル)プロピオニトリル]及び1,1’−アゾビス(1ーアセトキシー1−フェニルエタン)等が挙げられる。過硫酸塩としては、過硫酸アンモニウム、過硫酸カリウム及び過硫酸ナトリウム等が挙げられる。無機過酸化物としては、過硼酸塩及び過酸化水素等が挙げられる。レドックス触媒としては、アスコルビン酸−過酸化水素等が挙げられる。有機過酸化物としては、過酸化ベンゾイル等が挙げられる。これらの重合触媒は、単独又は混合して用いられてもよい。これらのうち、過硫酸塩及びアゾ化合物が好ましく、さらに好ましくは過硫酸塩及び2,2’−アゾビスイソブチロニトリル、特に好ましくは過硫酸アンモニウム、過硫酸カリウム及び過硫酸ナトリウムである。 A polymerization catalyst can be used for the polymerization. As the polymerization catalyst, an ordinary polymerization catalyst or the like is used, and azo compounds, persulfates, inorganic peroxides, redox catalysts, and organic peroxides are included. Examples of the azo compound include 2,2′-azobisisobutyronitrile, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile, 2, 2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-albonitrile), 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,2 ' -Azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile], 1,1'-azobis (1-acetoxy-1-phenylethane) and the like. Examples of the salt include ammonium persulfate, potassium persulfate, sodium persulfate, etc. Examples of the inorganic peroxide include perborate and hydrogen peroxide. Examples of the redox catalyst include ascorbic acid-hydrogen peroxide, etc. Examples of the organic peroxide include benzoyl peroxide, etc. These polymerization catalysts may be used alone or in combination. Of these, persulfates and azo compounds are preferred, more preferred are persulfates and 2,2′-azobisisobutyronitrile, and particularly preferred are ammonium persulfate, potassium persulfate, and sodium persulfate.
重合触媒を使用する場合、重合触媒の使用量(重量%)は、構成単量体の重量に基づいて、1〜30が好ましく、さらに好ましくは2〜25、特に好ましくは3〜20である。 When a polymerization catalyst is used, the amount (% by weight) of the polymerization catalyst used is preferably from 1 to 30, more preferably from 2 to 25, particularly preferably from 3 to 20, based on the weight of the constituent monomer.
また、必要によりラジカル重合用連鎖移動剤を使用してもよい。連鎖移動剤としては、チオール(n−ラウリルメルカプタン、メルカプトエタノール及びメルカプトプロパノール等)、チオカルボン酸(チオグリコール酸及びチオリンゴ酸等)、2級アルコール(イソプロパノ−ル等)、アミン(ジブチルアミン等)、次亜燐酸塩(次亜燐酸ナトリウム等)等が挙げられる。 Moreover, you may use the chain transfer agent for radical polymerization as needed. As the chain transfer agent, thiol (n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, etc.), thiocarboxylic acid (thioglycolic acid, thiomalic acid, etc.), secondary alcohol (isopropanol etc.), amine (dibutylamine etc.), Examples thereof include hypophosphites (sodium hypophosphite and the like).
連鎖移動剤を使用する場合、連鎖移動剤の使用量(重量%)は、構成単量体の重量に基づいて、0.01〜10が好ましく、さらに好ましくは0.05〜5、特に好ましくは0.1〜1である。 When the chain transfer agent is used, the amount (% by weight) of the chain transfer agent is preferably 0.01 to 10, more preferably 0.05 to 5, particularly preferably based on the weight of the constituent monomer. 0.1-1.
溶液重合及び懸濁重合の場合、溶媒としては、水(水道水、イオン交換水及び工業用水等)、アルコール溶剤(メタノール、エタノール及びイソプロピルアルコール等)及び/又は芳香族溶剤(トルエン及びキシレン等)等が使用できる。これらのうち、水、水及びアルコール溶剤の混合溶媒が好ましく、さらに好ましくは水及びアルコールの混合溶媒、特に好ましくはイオン交換水及びイソプロピルアルコールの混合溶媒である。
溶媒を使用する場合、この使用量(重量部)は、構成単量体100重量部に対して、5〜500が好ましく、さらに好ましくは10〜400、特に好ましくは15〜300である。
In the case of solution polymerization and suspension polymerization, the solvent includes water (tap water, ion exchange water, industrial water, etc.), alcohol solvent (methanol, ethanol, isopropyl alcohol, etc.) and / or aromatic solvent (toluene, xylene, etc.). Etc. can be used. Among these, water, a mixed solvent of water and an alcohol solvent are preferable, a mixed solvent of water and alcohol is more preferable, and a mixed solvent of ion-exchanged water and isopropyl alcohol is particularly preferable.
In the case of using a solvent, the amount (parts by weight) used is preferably 5 to 500, more preferably 10 to 400, and particularly preferably 15 to 300 with respect to 100 parts by weight of the constituent monomer.
重合反応温度は、40〜130℃程度が好ましく、重合反応時間は、1〜15時間程度が好ましい。 The polymerization reaction temperature is preferably about 40 to 130 ° C., and the polymerization reaction time is preferably about 1 to 15 hours.
なお、構成単量体の全量又は一部を滴下しながら重合してもよい。また、重合触媒の全量又は一部を滴下しながら重合してもよい。また、溶媒の全量又は一部を構成単量体又は重合触媒と共に滴下しながら重合してもよい。一方、溶媒の全量を重合槽に仕込んでおき溶媒を除去しながら重合してもよい。これらのうち、生産性の観点等から、構成単量体と重合触媒との全量を滴下する方法及び溶媒の一部を構成単量体又は重合触媒と共に滴下する方法が好ましく、さらに好ましくは構成単量体と重合触媒との全量を溶剤の一部と共に滴下する方法である。 In addition, you may superpose | polymerize, dripping the whole quantity or one part of a structural monomer. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a polymerization catalyst. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a solvent with a structural monomer or a polymerization catalyst. On the other hand, the entire amount of the solvent may be charged in a polymerization tank and polymerization may be performed while removing the solvent. Among these, from the viewpoint of productivity and the like, the method of dropping the whole amount of the constituent monomer and the polymerization catalyst and the method of dropping a part of the solvent together with the constituent monomer or the polymerization catalyst are preferable, and more preferably the constituent unit. In this method, the entire amount of the monomer and the polymerization catalyst is dropped together with a part of the solvent.
共重合体(X)の形態としては特に限定はなく、液状でも、固状でもよい。
共重合体(X)が液状の場合、水性溶媒に共重合体(X)が溶解又は分散した状態を意味する。この場合、共重合体(X)を懸濁重合又は溶液重合等によって得て、溶媒をすべて除去しないで得てもよいし、塊状重合等によって得た共重合体(X)を水性溶媒に溶解又は分散させて得てもよい。
水性溶媒としては、水、炭素数1〜6のアルコール(エチルアルコール、メチルアルコール、エチレングリコール及びジエチレングリコール等)及び炭素数1〜6のケトン(メチルイソブチルケトン及びアセトン等)等が挙げられ、これらは単独又は混合して用いてもよい。
The form of the copolymer (X) is not particularly limited, and may be liquid or solid.
When the copolymer (X) is liquid, it means a state in which the copolymer (X) is dissolved or dispersed in an aqueous solvent. In this case, the copolymer (X) may be obtained by suspension polymerization or solution polymerization without removing all the solvent, or the copolymer (X) obtained by bulk polymerization or the like may be dissolved in an aqueous solvent. Alternatively, it may be obtained by dispersing.
Examples of the aqueous solvent include water, alcohols having 1 to 6 carbon atoms (such as ethyl alcohol, methyl alcohol, ethylene glycol and diethylene glycol), and ketones having 1 to 6 carbon atoms (such as methyl isobutyl ketone and acetone). You may use individually or in mixture.
一方、共重合体(X)が固状の場合、共重合体(X)からなる固体であってもよく、液状の共重合体(X)を粉体に担持させた粉であってもよい。
共重合体(X)からなる固体の場合、塊状重合によって得てもよいし、共重合体(X)を含む溶液又は分散液を懸濁重合又は溶液重合等によって得てから、溶媒を除去することにより得てもよい。
共重合体(X)を含む溶液又は分散液から溶媒を除去する方法としては、乾燥粉砕法、凍結粉砕法、スプレイドライヤー法及びドラムドライヤー法等の公知の方法を用いることができる。これらのうち、乾燥粉砕法及びスプレイドライヤー法が好ましい。
固状の共重合体(X)の大きさ(mm;最大長)は、本発明の増粘剤の溶解性の観点等から、0.01〜5が好ましく、さらに好ましくは0.05〜3、特に好ましくは0.08〜1である。
液状の共重合体(X)を粉体に担持させる場合、粉体としては、後記の耐熱性無機酸化物、活性炭、炭酸カルシウム、ゼオライト、シラスバルーン及びベントナイト等が挙げられる。
これらの粉体に液状の共重合体(X)を担持させる方法としては、公知の撹拌混合機(リボンミキサー及びヘンシェルミキサー等)を使用して、粉体と液状の共重合体(X)とを撹拌混合する方法等が適用できる。
共重合体(X)の形態のうち、液状が好ましく、さらに好ましくは水性溶媒に共重合体(X)が溶解した状態である。
On the other hand, when the copolymer (X) is solid, it may be a solid made of the copolymer (X), or may be a powder having the liquid copolymer (X) supported on the powder. .
In the case of a solid comprising the copolymer (X), it may be obtained by bulk polymerization, or after the solution or dispersion containing the copolymer (X) is obtained by suspension polymerization or solution polymerization, the solvent is removed. May be obtained.
As a method for removing the solvent from the solution or dispersion containing the copolymer (X), known methods such as a dry pulverization method, a freeze pulverization method, a spray dryer method, and a drum dryer method can be used. Of these, the dry pulverization method and the spray dryer method are preferred.
The size (mm; maximum length) of the solid copolymer (X) is preferably from 0.01 to 5, more preferably from 0.05 to 3, from the viewpoint of the solubility of the thickener of the present invention. Especially preferably, it is 0.08-1.
When the liquid copolymer (X) is supported on a powder, examples of the powder include heat-resistant inorganic oxides, activated carbon, calcium carbonate, zeolite, shirasu balloon, and bentonite.
As a method for supporting the liquid copolymer (X) on these powders, the powder and the liquid copolymer (X) can be obtained by using a known stirring mixer (such as a ribbon mixer and a Henschel mixer). A method of stirring and mixing can be applied.
Among the forms of the copolymer (X), a liquid is preferable, and a state where the copolymer (X) is dissolved in an aqueous solvent is more preferable.
本発明の増粘剤には、共重合体(X)以外に、他の構成成分(界面活性剤及び/又は水性溶媒等)を含有してもよい。
界面活性剤としては、ノニオン型、カチオン型、アニオン型又は両性型の界面活性剤が使用できる。
In addition to the copolymer (X), the thickener of the present invention may contain other components (such as a surfactant and / or an aqueous solvent).
As the surfactant, a nonionic, cationic, anionic or amphoteric surfactant can be used.
ノニオン型界面活性剤としては、アルキルフェノールのアルキレンオキシド(アルキレンオキシドの炭素数2〜4;以下特記しない限り同様である。)付加体、高級脂肪酸アルキレンオキシド付加体、多価アルコール脂肪酸エステル、高級アルキルアミンのアルキレンオキシド付加体、高級脂肪酸アミドのアルキレンオキシド付加体、アセチレングリコールのアルキレンオキシド付加体及びポリオキシアルキレン変性シリコーン(ポリエーテル変性シリコーン)等が挙げられる。 Nonionic surfactants include alkylene oxides of alkylphenols (alkylene oxides having 2 to 4 carbon atoms; the same unless otherwise specified), higher fatty acid alkylene oxide adducts, polyhydric alcohol fatty acid esters, higher alkyl amines. Alkylene oxide adducts of higher fatty acid amides, alkylene oxide adducts of acetylene glycol, and polyoxyalkylene-modified silicones (polyether-modified silicones).
カチオン型界面活性剤としては、高級アルキルアミン塩、高級アルキルアミンアルキレンオキシド付加体、ソロミンA型カチオン界面活性剤、サパミンA型カチオン界面活性剤、アーコベルA型カチオン界面活性剤、イミダゾリン型カチオン界面活性剤、高級アルキルトリメチルアンモニウム塩、高級アルキルジメチルベンジルアンモニウム塩、サパミン型第4級アンモニウム塩及びピリジニウム塩等が挙げられる。 Cationic surfactants include higher alkylamine salts, higher alkylamine alkylene oxide adducts, solomin A type cationic surfactants, sapamin A type cationic surfactants, Arcobel A type cationic surfactants, and imidazoline type cationic surfactants. Agents, higher alkyltrimethylammonium salts, higher alkyldimethylbenzylammonium salts, sapamine-type quaternary ammonium salts and pyridinium salts.
アニオン型界面活性剤としては、脂肪酸塩、α−オレフィンスルホン酸塩、アルキルベンゼンスルホン酸とその塩、アルキル硫酸エステル塩、アルキルエーテル硫酸エステル塩、N−アシルアルキルタウリン塩及びアルキルスルホコハク酸塩等が挙げられる。 Examples of the anionic surfactant include fatty acid salts, α-olefin sulfonates, alkylbenzene sulfonic acids and salts thereof, alkyl sulfate esters, alkyl ether sulfates, N-acyl alkyl taurates, and alkyl sulfosuccinates. It is done.
両性型界面活性剤としては、高級アルキルアミノプロピオン酸塩及び高級アルキルジメチルベタイン等が挙げられる。 Examples of amphoteric surfactants include higher alkylaminopropionates and higher alkyldimethylbetaines.
界面活性剤を含有する場合、この含有量(重量%)は、共重合体(X)の重量に基づいて、0.1〜20が好ましく、さらに好ましくは0.5〜10、特に好ましくは1〜5である。この範囲であると増粘効果がさらに良好となる。 When the surfactant is contained, the content (% by weight) is preferably 0.1 to 20, more preferably 0.5 to 10, particularly preferably 1 based on the weight of the copolymer (X). ~ 5. Within this range, the thickening effect is further improved.
水性溶媒としては、上記のものが挙げられる。
水性溶媒を含有する場合、この含有量(重量部)は、共重合体(X)100重量部に対して、10〜1000が好ましく、さらに好ましくは50〜900、特に好ましくは100〜600である。
Examples of the aqueous solvent include those described above.
When the aqueous solvent is contained, the content (parts by weight) is preferably 10 to 1000, more preferably 50 to 900, and particularly preferably 100 to 600 with respect to 100 parts by weight of the copolymer (X). .
本発明の増粘剤に他の構成成分を含有する場合、本発明の増粘剤は、共重合体(X)と、他の構成成分とを均一混合(均一溶解又は均一分散)することにより得られる。 When the thickener of the present invention contains other components, the thickener of the present invention is obtained by uniformly mixing (uniformly dissolving or uniformly dispersing) the copolymer (X) and other components. can get.
本発明の増粘剤は、貴金属を担持した耐熱性無機酸化物及び分散媒を含む排ガス浄化触媒用スラリーの粘度を効果的に上昇できる。本発明の増粘剤以外のものを用いても、このスラリーの粘度を効果的に上昇させることができない。これは、本発明の増粘剤に含有される共重合体の構成単量体の種類及びこの重量平均分子量に基づくものと考えられる。たとえば、共重合体を構成する単量体を他の単量体に変更したり、重量平均分子量が規定範囲から外れたりすると、もはや本発明の効果は得られない。 The thickener of the present invention can effectively increase the viscosity of a slurry for exhaust gas purification catalyst containing a heat-resistant inorganic oxide carrying a noble metal and a dispersion medium. Even if a material other than the thickener of the present invention is used, the viscosity of the slurry cannot be effectively increased. This is considered to be based on the type of the constituent monomer of the copolymer contained in the thickener of the present invention and the weight average molecular weight. For example, if the monomer constituting the copolymer is changed to another monomer, or the weight average molecular weight is out of the specified range, the effect of the present invention can no longer be obtained.
<排ガス浄化触媒用スラリー>
耐熱性無機酸化物としては、高温度(900℃以上)でも劣化することなく、貴金属を担持できれば制限はなく、ジルコニア、アルミナ、シリカ、チタニア、マグネシア及びセリアからなる郡より選ばれる少なくとも一種等が挙げられる。
<Slurry for exhaust gas purification catalyst>
The heat-resistant inorganic oxide is not limited as long as it can support a noble metal without being deteriorated even at a high temperature (900 ° C. or higher), and includes at least one selected from the group consisting of zirconia, alumina, silica, titania, magnesia and ceria. Can be mentioned.
耐熱性無機酸化物の体積平均粒子径(μm)は、触媒性能の観点から、0.1〜100が好ましく、さらに好ましくは0.2〜50、特に好ましくは0.3〜10である。
なお、体積平均粒子径は、JIS Z8825−1:2001に準拠したレーザー回折式粒度分析計{例えば、Leeds&Northrup社製Microtrac Model No.MT3300EX}を用い、測定試料濃度0.1重量%となるように水に測定試料を添加して調製した測定分散液について、測定温度25±5℃で測定して、50%積算体積平均粒子径として求められる。
The volume average particle diameter (μm) of the heat-resistant inorganic oxide is preferably 0.1 to 100, more preferably 0.2 to 50, and particularly preferably 0.3 to 10 from the viewpoint of catalyst performance.
In addition, the volume average particle diameter is a laser diffraction particle size analyzer conforming to JIS Z8825-1: 2001 (for example, Microtrac Model No. manufactured by Lees & Northrup). MT3300EX}, a measurement dispersion prepared by adding a measurement sample to water so that the measurement sample concentration is 0.1% by weight, measured at a measurement temperature of 25 ± 5 ° C., and 50% cumulative volume average particle diameter As required.
貴金属としては、窒素酸化物(NOX)を窒素(N2)に還元でき、また、一酸化炭素(CO)を二酸化炭素(CO2)に酸化でき、炭化水素(ハイドロカーボン)を二酸化炭素及び水に酸化することができれば制限なく、いわゆる三元触媒等が使用でき、プラチナ、パラジウム及びロジウム等が挙げられる。 As the noble metal, nitrogen oxide (NO x ) can be reduced to nitrogen (N 2 ), carbon monoxide (CO) can be oxidized to carbon dioxide (CO 2 ), and hydrocarbon (hydrocarbon) can be converted to carbon dioxide and So-called three-way catalysts can be used without limitation as long as they can be oxidized to water, and examples thereof include platinum, palladium and rhodium.
貴金属の担持量(重量%)は、排ガスの種類、排ガス処理量等により適宜決定できるが、耐熱性無機酸化物の重量に基づいて、0.001〜20が好ましく、さらに好ましくは0.01〜15である。 The amount (% by weight) of the noble metal supported can be appropriately determined depending on the type of exhaust gas, the amount of exhaust gas treated, etc., but is preferably 0.001 to 20 based on the weight of the heat-resistant inorganic oxide, and more preferably 0.01 to 15.
耐熱性無機酸化物に貴金属を担持させる方法としては、公知の方法(たとえば、含浸法;アルミナやシリカ等の無機酸化物の担体に触媒金属溶液を含浸させて担持する方法)等をそのまま適用できる。 As a method for supporting a noble metal on a heat-resistant inorganic oxide, a known method (for example, an impregnation method; a method of impregnating and supporting a catalyst metal solution on an inorganic oxide carrier such as alumina or silica) can be applied as it is. .
分散媒としては、水及び水と水溶性有機溶媒との混合溶媒が含まれる。これらのうち、水が好ましい。 Examples of the dispersion medium include water and a mixed solvent of water and a water-soluble organic solvent. Of these, water is preferred.
水溶性有機溶媒としては、炭素数1〜3のアルコール(メタノール、エタノール、イソプロパノール、エチレングリコール及びプロピレングリコール等)、炭素数1〜3のケトン(アセトン、メチルエチルケトン及びジメチルスルホキシド等)、炭素数4〜6のエーテル(ジエチルエーテル、テトラハイドロフラン、ジオキサン、ジエチレングリコール及びトリエチレングリコール等)が含まれる。 Examples of the water-soluble organic solvent include alcohols having 1 to 3 carbon atoms (such as methanol, ethanol, isopropanol, ethylene glycol, and propylene glycol), ketones having 1 to 3 carbon atoms (such as acetone, methyl ethyl ketone, and dimethyl sulfoxide), and those having 4 to 4 carbon atoms. 6 ethers such as diethyl ether, tetrahydrofuran, dioxane, diethylene glycol and triethylene glycol.
増粘剤の含有量は、上記の(共)重合体の含有量(重量%)が、耐熱性無機酸化物の重量に基づいて、0.01〜15となる量が好ましく、さらに好ましくは0.05〜10となる量、特に好ましくは0.1〜5となる量、最も好ましくは2〜3となる量である。この範囲であると、増粘効果がさらに良好となる。 The content of the thickener is preferably such that the content (% by weight) of the (co) polymer is 0.01 to 15 based on the weight of the heat-resistant inorganic oxide, more preferably 0. An amount of 0.05 to 10, particularly preferably 0.1 to 5, and most preferably an amount of 2 to 3. Within this range, the thickening effect is further improved.
分散媒の含有量は、触媒仕様によって適宜決定できるが、耐熱性無機酸化物100重量部に対して100〜900重量部が好ましい。 Although content of a dispersion medium can be suitably determined with a catalyst specification, 100-900 weight part is preferable with respect to 100 weight part of heat resistant inorganic oxides.
本発明の排ガス浄化触媒用スラリーには、上記の増粘剤、貴金属を担持した耐熱性無機酸化物及び分散媒以外に、他の添加剤(消泡剤、本発明の増粘剤以外の増粘剤、分散剤等)を含有してもよい。 In the slurry for exhaust gas purification catalyst of the present invention, in addition to the above thickener, the heat-resistant inorganic oxide supporting the noble metal and the dispersion medium, other additives (antifoaming agent, thickener other than the thickener of the present invention) are added. (Viscous agent, dispersant, etc.) may be contained.
本発明の排ガス浄化触媒用スラリーは、増粘剤、貴金属を担持した耐熱性無機酸化物及び分散媒、並びに必要に応じて他の添加剤を均一混合分散できれば、製造方法に制限はなく、公知の混合分散機でスラリー化することにより得ることができる。スラリー化する際、溶媒が蒸発しないように、適宜、密閉にしたり、冷却したりできる。 The slurry for the exhaust gas purifying catalyst of the present invention is not limited in its production method as long as it can uniformly mix and disperse the thickener, the heat-resistant inorganic oxide supporting the noble metal and the dispersion medium, and other additives as required. It can be obtained by slurrying with a mixing and dispersing machine. When slurrying, it can be appropriately sealed or cooled so that the solvent does not evaporate.
排ガス浄化触媒用スラリーの粘度(mPa・s、25℃)は、せん断速度が380s−1の場合、50〜400が好ましく、さらに好ましくは70〜350、特に好ましくは100〜300であり、せん断速度が4s−1の場合、500〜8000が好ましく、さらに好ましくは800〜7500、特に好ましくは1000〜7000である。
なお、粘度は、せん断速度380s−1又は4s−1で回転粘度計(たとえば、レオメーターPhysica MCR301(Anton Paar社製)を用いて測定される。
The viscosity (mPa · s, 25 ° C.) of the exhaust gas purifying catalyst slurry is preferably 50 to 400, more preferably 70 to 350, particularly preferably 100 to 300 when the shear rate is 380 s −1 , and the shear rate. Is 4 s −1 , 500 to 8000 is preferable, 800 to 7500 is more preferable, and 1000 to 7000 is particularly preferable.
The viscosity is measured using a rotational viscometer (for example, a rheometer Physica MCR301 (manufactured by Anton Paar)) at a shear rate of 380 s −1 or 4 s −1 .
<排ガス浄化触媒の製造方法>
スラリー化工程(1)において、上記の増粘剤、貴金属を担持した耐熱性無機酸化物及び分散媒を均一混合分散してスラリーを得るが、均一混合分散は、上記のとおり、公知の混合分散機で行うことができる。
<Method for producing exhaust gas purification catalyst>
In the slurrying step (1), the above thickener, the heat-resistant inorganic oxide supporting the noble metal, and the dispersion medium are uniformly mixed and dispersed to obtain a slurry. Can be done on the machine.
塗布工程(2)において、基材としては、耐熱性(900〜1000℃程度まで)があり、耐腐蝕性(排ガスに対しての腐蝕がない)があれば制限なく、セラミックス及びステンレス等が好適に使用できる。セラミックスとしては、コージェライト(2MgO・2Al2O3・5SiO2)等が挙げられる。基材の形状は、用途等により適宜決定できる。 In the coating step (2), the base material has heat resistance (up to about 900 to 1000 ° C.) and is not limited as long as it has corrosion resistance (no corrosion against exhaust gas), and ceramics and stainless steel are preferable. Can be used for Examples of the ceramic include cordierite (2MgO · 2Al 2 O 3 · 5SiO 2 ). The shape of the substrate can be appropriately determined depending on the application.
排ガス浄化触媒が内燃機関用の場合、基材としては、入口端側と出口端側との間で連通するモノリス型基材が好ましく、さらに好ましくは入口端側と出口端側との間で連通するハニカム型基材である。 When the exhaust gas purification catalyst is for an internal combustion engine, the base material is preferably a monolith type base material that communicates between the inlet end side and the outlet end side, and more preferably communicates between the inlet end side and the outlet end side. It is a honeycomb type substrate.
塗布方法としては、基材に、スラリーを塗布して塗布基材を得ることができれば制限はない。
基材が入口端側と出口端側との間で連通するモノリス型基材の場合、塗布工程(2)は、入口端側から出口端側に向けてスラリーを移送させる方法により塗布する移送塗布工程(21)、又はスラリーに基材を浸漬する方法により塗布する浸漬塗布工程(22)であってもよい。これらのうち、移送塗布工程(21)が好ましく、さらに好ましくは出口端側を入口端側よりも負圧にし、入口端側と出口端側との圧力差により、入口端側から出口端側に向けてスラリーを移送させる方法により塗布する移送塗布工程である。移送塗布工程(21)としては、特開2008−302304号公報に開示された方法が参考となる。
なお、入口端側と出口端側との圧力差によってスラリーを移送させる場合、出口端側を減圧してもよく、入口端側を加圧してもよく、さらに、出口端側を減圧し、入口端側を加圧してもよい。
塗布量は、排ガスの種類、排ガス処理量等により適宜決定できる。
As a coating method, there is no limitation as long as the coated substrate can be obtained by applying the slurry to the substrate.
When the base material is a monolith type base material that communicates between the inlet end side and the outlet end side, the coating step (2) is a transfer coating in which the slurry is applied by a method of transferring the slurry from the inlet end side toward the outlet end side. It may be a step (21) or a dip coating step (22) of coating by a method of immersing the substrate in the slurry. Of these, the transfer coating step (21) is preferable, and more preferably, the outlet end side is made more negative than the inlet end side, and the pressure difference between the inlet end side and the outlet end side causes the inlet end side to the outlet end side. This is a transfer coating process in which the slurry is coated by a method of transporting the slurry toward it. As the transfer coating step (21), the method disclosed in JP 2008-302304 A is a reference.
When the slurry is transferred by the pressure difference between the inlet end side and the outlet end side, the outlet end side may be depressurized, the inlet end side may be pressurized, and the outlet end side is depressurized. You may pressurize an end side.
The coating amount can be appropriately determined depending on the type of exhaust gas, the exhaust gas treatment amount, and the like.
焼成工程(3)において、乾燥条件は塗布基材を乾燥できれば制限はなく、公知の条件(たとえば、240〜260℃、0.5〜2時間)が適用できる。また、焼成条件は塗布基材を乾燥した後これを焼成して有機成分を焼失させ、酸化できるものを酸化できれば制限はなく、公知の条件(たとえば、450〜900℃、0.5〜2時間)が適用できる。 In the firing step (3), the drying conditions are not limited as long as the coated substrate can be dried, and known conditions (for example, 240 to 260 ° C., 0.5 to 2 hours) can be applied. The baking conditions are not limited as long as the coated substrate is dried and then baked to burn off the organic components, and those that can be oxidized can be oxidized. Known conditions (for example, 450 to 900 ° C., 0.5 to 2 hours) ) Is applicable.
本発明の製造方法で製造される排ガス浄化触媒は、浄化すべき排ガスであれば制限なく適用でき、内燃機関、工場、産業廃棄物処理場等から排出される排ガスに好適である。これらのうち、内燃機関から排出される排ガスに最適である。
本発明の製造方法で製造される排ガス浄化用触媒を搭載した内燃機関は、自動車、自動二輪、農業機械、土木建築機械等に搭載できる。
The exhaust gas purification catalyst produced by the production method of the present invention can be applied without limitation as long as it is an exhaust gas to be purified, and is suitable for exhaust gas discharged from internal combustion engines, factories, industrial waste treatment plants, and the like. Of these, it is most suitable for exhaust gas discharged from an internal combustion engine.
The internal combustion engine equipped with the exhaust gas purification catalyst produced by the production method of the present invention can be installed in an automobile, a motorcycle, an agricultural machine, a civil engineering construction machine, or the like.
以下、特記しない限り、部は重量部を、%は重量%を意味する。 Hereinafter, unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
<実施例1>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水500部、イソプロピルアルコール100部及び2−メルカプトエタノール0.5部を投入し、密閉下で攪拌しながら、アクリル酸80部、アクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:23)エステル270部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、本発明の増粘剤(1)[アクリル酸(82モル%)−アクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:23)エステル(18モル%)共重合体(x1)]を得た。なお、共重合体(x1)の重量平均分子量は28,000であった。
<Example 1>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 500 parts of ion-exchanged water, 100 parts of isopropyl alcohol and 0.5 part of 2-mercaptoethanol are added, and 80 parts of acrylic acid and acrylic are stirred while being sealed. 270 parts of acid methoxypolyoxyethylene (oxyethylene polymerization degree: 23) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from a separate dropping line at a constant rate over 3 hours, and reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of the dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (1) [acrylic acid (82 mol%)-methoxypolyoxyethylene acrylate (degree of polymerization of oxyethylene: 23) ester (18 mol%) copolymer (x1)] was obtained. The weight average molecular weight of the copolymer (x1) was 28,000.
重量平均分子量(Mw)は、分子量既知の(ポリ)エチレングリコールを標準物質として、ゲルパーミエーションクロマトグラフィー(GPC)法(カラム温度40℃、溶離液 メタノール:イオン交換水:酢酸ナトリウム=800:1200:15(重量比)、流速0.8ml/分、試料濃度:0.4重量%溶離液溶液。)で測定した(以下、同じである。)。 The weight average molecular weight (Mw) is a gel permeation chromatography (GPC) method (column temperature 40 ° C., eluent methanol: ion-exchanged water: sodium acetate = 800: 1200 using (poly) ethylene glycol of known molecular weight as a standard substance. : 15 (weight ratio), flow rate 0.8 ml / min, sample concentration: 0.4 wt% eluent solution) (hereinafter the same).
<実施例2>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水600部、イソプロピルアルコール70部及び2−メルカプトエタノール2.5部を投入し、密閉下で攪拌しながら、アクリル酸300部、アクリル酸エトキシポリオキシエチレン(オキシエチレンの重合度:2)エステル25部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、本発明の増粘剤(2)[アクリル酸(97モル%)−アクリル酸エトキシポリオキシエチレン(オキシエチレンの重合度:2)エステル(3モル%)共重合体(x2)]を得た。なお、共重合体(x2)の重量平均分子量は11,000であった。
<Example 2>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 600 parts of ion-exchanged water, 70 parts of isopropyl alcohol and 2.5 parts of 2-mercaptoethanol are added, and 300 parts of acrylic acid and acrylic are stirred while being sealed. 25 parts of acid ethoxypolyoxyethylene (oxyethylene polymerization degree: 2) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from each separate dropping line at a constant rate for 3 hours to be reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of the dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (2) [acrylic acid (97 mol%)-acrylic acid ethoxypolyoxyethylene (degree of polymerization of oxyethylene: 2) ester (3 mol%) copolymer (x2)] was obtained. The weight average molecular weight of the copolymer (x2) was 11,000.
<実施例3>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水500部、イソプロピルアルコール70部及び2−メルカプトエタノール2部を投入し、密閉下で攪拌しながら、アクリル酸168部、アクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:9)エステル59部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、本発明の増粘剤(3)[アクリル酸(95モル%)−アクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:9)エステル(5モル%)共重合体(x3)]を得た。なお、共重合体(x3)の重量平均分子量は12,000であった。
<Example 3>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 500 parts of ion-exchanged water, 70 parts of isopropyl alcohol and 2 parts of 2-mercaptoethanol are added, and 168 parts of acrylic acid and methoxy acrylate are stirred while being sealed. 59 parts of polyoxyethylene (oxyethylene polymerization degree: 9) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from a separate dropping line at a constant rate over 3 hours, and reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of the dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (3) [acrylic acid (95 mol%)-methoxypolyoxyethylene acrylate (degree of polymerization of oxyethylene: 9) ester (5 mol%) copolymer (x3)] was obtained. The weight average molecular weight of the copolymer (x3) was 12,000.
<実施例4>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水500部、イソプロピルアルコール60部及び2−メルカプトエタノール1部を投入し、密閉下で攪拌しながら、メタクリル酸50部、メタクリル酸オクタデシルオキシポリオキシエチレン(オキシエチレンの重合度:30)エステル184部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、本発明の増粘剤(4)[メタクリル酸(84モル%)−メタクリル酸オクタデシルオキシポリオキシエチレン(オキシエチレンの重合度:30)エステル(16モル%)共重合体(x4)]を得た。なお、共重合体(x4)の重量平均分子量は26,000であった。
<Example 4>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 500 parts of ion-exchanged water, 60 parts of isopropyl alcohol and 1 part of 2-mercaptoethanol are charged, and 50 parts of methacrylic acid and octadecyl methacrylate are stirred while sealed. 184 parts of oxypolyoxyethylene (degree of polymerization of oxyethylene: 30) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from a separate dropping line at a constant rate over 3 hours, and reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of the dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (4) [methacrylic acid (84 mol%)-octadecyloxypolyoxyethylene methacrylate (degree of polymerization of oxyethylene: 30) ester (16 mol%) copolymer (x4)] was obtained. The weight average molecular weight of the copolymer (x4) was 26,000.
<実施例5>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水500部、イソプロピルアルコール120部及び2−メルカプトエタノール3部を投入し、密閉下で攪拌しながら、メタクリル酸40部、メタクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:90)エステル470部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、本発明の増粘剤(5)[メタクリル酸(80モル%)−メタクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:90)エステル(20モル%)共重合体(x5)]を得た。なお、共重合体(x5)の重量平均分子量は10,000であった。
<Example 5>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 500 parts of ion-exchanged water, 120 parts of isopropyl alcohol and 3 parts of 2-mercaptoethanol are added, and 40 parts of methacrylic acid and methoxy methacrylate are stirred while being sealed. 470 parts of polyoxyethylene (oxyethylene polymerization degree: 90) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from a separate dropping line at a constant rate over 3 hours, and reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of the dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (5) [methacrylic acid (80 mol%)-methacrylic acid methoxypolyoxyethylene (degree of polymerization of oxyethylene: 90) ester (20 mol%) copolymer (x5)] was obtained. The copolymer (x5) had a weight average molecular weight of 10,000.
<実施例6>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水500部、イソプロピルアルコール100部及び2−メルカプトエタノール0.5部を投入し、密閉下で攪拌しながら、アクリル酸280部、アクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:23)エステル180部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、本発明の増粘剤(6)[アクリル酸(96モル%)−アクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:23)エステル(4モル%)共重合体(x6)]を得た。なお、共重合体(x6)の重量平均分子量は30,000であった。
<Example 6>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 500 parts of ion-exchanged water, 100 parts of isopropyl alcohol and 0.5 part of 2-mercaptoethanol are added, and 280 parts of acrylic acid, acrylic while stirring in a sealed state. 180 parts of acid methoxypolyoxyethylene (oxyethylene polymerization degree: 23) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from each separate dropping line at a constant rate for 3 hours to be reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of the dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (6) [acrylic acid (96 mol%)-acrylic acid methoxypolyoxyethylene (degree of polymerization of oxyethylene: 23) ester (4 mol%) copolymer (x6)] was obtained. The weight average molecular weight of the copolymer (x6) was 30,000.
<比較例1>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水500部、イソプロピルアルコール100部及び2−メルカプトエタノール2部を投入し、密閉下で攪拌しながら、アクリル酸400部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、比較用の増粘剤(7)[ポリアクリル酸(x7)]を得た。なお、ポリアクリル酸(x7)の重量平均分子量は15,000であった。
<Comparative Example 1>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 500 parts of ion-exchanged water, 100 parts of isopropyl alcohol and 2 parts of 2-mercaptoethanol are added, and while stirring in a sealed state, 400 parts of acrylic acid and 40% excess are added. 100 parts of sodium sulfate aqueous solution was dropped from each separate dropping line at a constant rate over 3 hours to be reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (7) [polyacrylic acid (x7)] was obtained. The weight average molecular weight of polyacrylic acid (x7) was 15,000.
<比較例2>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水600部、イソプロピルアルコール250部及び2−メルカプトエタノール1.5部を投入し、密閉下で攪拌しながら、メタクリル酸100部、メタクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:23)エステル550部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、比較用の増粘剤(8)[メタクリル酸(70モル%)−メタクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:23)エステル(30モル%)共重合体(x8)]を得た。なお、共重合体(x8)の重量平均分子量は15,000であった。
<Comparative example 2>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer, and a thermometer, 600 parts of ion-exchanged water, 250 parts of isopropyl alcohol and 1.5 parts of 2-mercaptoethanol are added, and 100 parts of methacrylic acid, 550 parts of acid methoxypolyoxyethylene (oxyethylene polymerization degree: 23) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from a separate dropping line at a constant rate over 3 hours, and reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (8) [methacrylic acid (70 mol%)-methoxypolyoxyethylene methacrylate (polymerization degree of oxyethylene: 23) ester (30 mol%) copolymer (x8)] was obtained. The weight average molecular weight of the copolymer (x8) was 15,000.
<比較例3>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水500部、イソプロピルアルコール10部及び2−メルカプトエタノール0.3部を投入し、密閉下で攪拌しながら、メタクリル酸50部、メタクリル酸オクタデシルオキシポリオキシエチレン(オキシエチレンの重合度:30)エステル200部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、比較用の増粘剤(9)[メタクリル酸(83モル%)−メタクリル酸オクタデシルオキシポリオキシエチレン(オキシエチレンの重合度:30)エステル(17モル%)共重合体(x9)]を得た。なお、共重合体(x9)の重量平均分子量は50,000であった。
<Comparative Example 3>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 500 parts of ion-exchanged water, 10 parts of isopropyl alcohol and 0.3 part of 2-mercaptoethanol are added, and 50 parts of methacrylic acid, 200 parts of acid octadecyloxypolyoxyethylene (polymerization degree of oxyethylene: 30) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from a separate dropping line at a constant rate over 3 hours, and reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (9) [methacrylic acid (83 mol%)-octadecyloxypolyoxyethylene methacrylate (degree of polymerization of oxyethylene: 30) ester (17 mol%) copolymer (x9)] was obtained. The weight average molecular weight of the copolymer (x9) was 50,000.
<比較例4>
滴下ライン、攪拌装置及び温度計付きの耐圧反応容器にイオン交換水100部、イソプロピルアルコール300部及び2−メルカプトエタノール4部を投入し、密閉下で攪拌しながら、メタクリル酸70部、メタクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:9)エステル70部及び40%過硫酸ナトリウム水溶液100部をそれぞれ別々の滴下ラインから3時間かけて一定速度で滴下して反応させた。反応温度は80〜100℃を保った。滴下終了後、3時間95〜100℃に保った後、150部のイオン交換水を滴下しながらイソプロピルアルコールを減圧除去した後、イオン交換水で濃度を30%に調整して、比較用の増粘剤(10)[メタクリル酸(85モル%)−メタクリル酸メトキシポリオキシエチレン(オキシエチレンの重合度:9)エステル(15モル%)共重合体(x10)]を得た。なお、共重合体(x10)の重量平均分子量は7,000であった。
<Comparative Example 4>
100 parts of ion-exchanged water, 300 parts of isopropyl alcohol and 4 parts of 2-mercaptoethanol are put into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, and 70 parts of methacrylic acid and methoxymethacrylate are stirred with stirring in a sealed state. 70 parts of polyoxyethylene (oxyethylene polymerization degree: 9) ester and 100 parts of 40% sodium persulfate aqueous solution were dropped from a separate dropping line at a constant rate over 3 hours and reacted. The reaction temperature was maintained at 80-100 ° C. After the completion of dropping, the temperature is kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, and then the concentration is adjusted to 30% with ion-exchanged water. Sticky agent (10) [methacrylic acid (85 mol%)-methoxypolyoxyethylene methacrylate (polymerization degree of oxyethylene: 9) ester (15 mol%) copolymer (x10)] was obtained. The copolymer (x10) had a weight average molecular weight of 7,000.
<実施例7>
分散媒(1){イオン交換水}80部、アルミナ(微粒子)1部、セリア−ジルコニア複合酸化物(微粒子)9.5部及びPGM(白金族金属:ロジウム、パラジウム、白金)を担持したアルミナ(微粒子)9.5部を均一に混合してスラリー(a1)を得た後、このスラリー(a1)をビーズミルにて湿式粉砕(40℃以下、約30分)してスラリー(b1)を得た。スラリー(b1)100部と実施例1で得た増粘剤(1)1.4とを均一混合して、本発明の排ガス浄化触媒用スラリー(c1)を得た。
<Example 7>
Dispersion medium (1) {ion-exchanged water} 80 parts, alumina (fine particles) 1 part, ceria-zirconia composite oxide (fine particles) 9.5 parts and alumina supporting PGM (platinum group metals: rhodium, palladium, platinum) After uniformly mixing 9.5 parts of (fine particles) to obtain a slurry (a1), the slurry (a1) was wet pulverized (below 40 ° C., about 30 minutes) with a bead mill to obtain a slurry (b1). It was. 100 parts of the slurry (b1) and the thickener (1) 1.4 obtained in Example 1 were uniformly mixed to obtain an exhaust gas purification catalyst slurry (c1) of the present invention.
<実施例8>
「実施例1で得た増粘剤(1)1.4部」を「実施例2で得た増粘剤(2)2部」に変更したこと以外、実施例7と同様にして、本発明の排ガス浄化用スラリー(c2)を得た。
<Example 8>
In the same manner as in Example 7, except that “1.4 parts of thickener (1) obtained in Example 1” was changed to “2 parts of thickener (2) obtained in Example 2”. An exhaust gas-purifying slurry (c2) of the invention was obtained.
<実施例9>
「実施例1で得た増粘剤(1)1.4部」を「実施例3で得た増粘剤(3)1.4部」に変更したこと以外、実施例7と同様にして、本発明の排ガス浄化用スラリー(c3)を得た。
<Example 9>
Except that 1.4 parts of the thickener (1) obtained in Example 1 was changed to 1.4 parts of the thickener (3) obtained in Example 3, the same as in Example 7. Thus, an exhaust gas purifying slurry (c3) of the present invention was obtained.
<実施例10>
「実施例1で得た増粘剤(1)1.4部」を「実施例4で得た増粘剤(4)2部」に変更したこと以外、実施例7と同様にして、本発明の排ガス浄化用スラリー(c4)を得た。
<Example 10>
In the same manner as in Example 7, except that “1.4 parts of thickener (1) obtained in Example 1” was changed to “2 parts of thickener (4) obtained in Example 4”. An exhaust gas-purifying slurry (c4) of the invention was obtained.
<実施例11>
「実施例1で得た増粘剤(1)1.4部」を「実施例5で得た増粘剤(5)1.4部」に変更したこと以外、実施例7と同様にして、本発明の排ガス浄化用スラリー(c5)を得た。
<Example 11>
Except for changing “Thickener (1) 1.4 parts obtained in Example 1” to “1.4 parts Thickener (5) obtained in Example 5”, in the same manner as Example 7. Thus, an exhaust gas purifying slurry (c5) of the present invention was obtained.
<実施例12>
「実施例1で得た増粘剤(1)1.4部」を「実施例6で得た増粘剤(6)2部」に変更したこと以外、実施例7と同様にして、本発明の排ガス浄化用スラリー(c6)を得た。
<Example 12>
In the same manner as in Example 7, except that “1.4 parts of thickener (1) obtained in Example 1” was changed to “2 parts of thickener (6) obtained in Example 6”. An exhaust gas-purifying slurry (c6) of the invention was obtained.
<比較例5>
「実施例1で得た増粘剤(1)」を用いなかったこと以外、実施例7と同様にして、比較用の排ガス浄化用スラリー(c7)を得た。
<Comparative Example 5>
A comparative exhaust gas purifying slurry (c7) was obtained in the same manner as in Example 7 except that the “thickener (1) obtained in Example 1” was not used.
<比較例6>
「実施例1で得た増粘剤(1)1.4部」を「比較例1で得た増粘剤(7)1.4部」に変更したこと以外、実施例7と同様にして、比較用の排ガス浄化用スラリー(c8)を得た。
<Comparative Example 6>
Except for changing “Thickener (1) 1.4 parts obtained in Example 1” to “1.4 parts Thickener (7) obtained in Comparative Example 1”, in the same manner as Example 7. A comparative exhaust gas purification slurry (c8) was obtained.
<比較例7>
「実施例1で得た増粘剤(1)1.4部」を「比較例2で得た増粘剤(8)2部」に変更したこと以外、実施例7と同様にして、比較用の排ガス浄化用スラリー(c9)を得た。
<Comparative Example 7>
A comparison was made in the same manner as in Example 7, except that “1.4 parts of thickener (1) obtained in Example 1” was changed to “2 parts of thickener (8) obtained in Comparative Example 2”. An exhaust gas-purifying slurry (c9) was obtained.
<比較例8>
「実施例1で得た増粘剤(1)1.4部」を「比較例3で得た増粘剤(9)1.4部」に変更したこと以外、実施例7と同様にして、比較用の排ガス浄化用スラリー(c10)を得た。
<Comparative Example 8>
Except for changing “Thickener (1) 1.4 parts obtained in Example 1” to “1.4 parts Thickener (9) obtained in Comparative Example 3”, in the same manner as Example 7. A comparative exhaust gas purification slurry (c10) was obtained.
<比較例9>
「実施例1で得た増粘剤(1)1.4部」を「比較例4で得た増粘剤(10)2部」に変更したこと以外、実施例7と同様にして、比較用の排ガス浄化用スラリー(c11)を得た。
<Comparative Example 9>
A comparison was made in the same manner as in Example 7 except that “1.4 parts of thickener (1) obtained in Example 1” was changed to “2 parts of thickener (10) obtained in Comparative Example 4”. An exhaust gas purification slurry (c11) was obtained.
<実施例13>
コージェライト(2MgO・2Al2O3・5SiO2)製のハニカム型基材(入口端側と出口端側との間で連通している。図1参照。)の出口端側を減圧にすると共に、入口端側を実施例7で得た排ガス浄化触媒用スラリー(c1)に付けて、ハニカム内部にスラリーを塗布して、塗布基材(1)を得た。
塗布基材(1)を250℃で1時間乾燥した後、続いて、500℃で1時間焼成して、排ガス浄化触媒(1)を得た。
<Example 13>
While reducing the pressure on the outlet end side of the honeycomb type base material (connected between the inlet end side and the outlet end side, see FIG. 1) made of cordierite (2MgO · 2Al 2 O 3 · 5SiO 2 ) The inlet end side was attached to the slurry for exhaust gas purification catalyst (c1) obtained in Example 7, and the slurry was applied to the inside of the honeycomb to obtain the coated substrate (1).
The coated substrate (1) was dried at 250 ° C. for 1 hour and then calcined at 500 ° C. for 1 hour to obtain an exhaust gas purification catalyst (1).
<実施例14〜18>
排ガス浄化触媒用スラリー(c1)を排ガス浄化触媒用スラリー(c2)〜(c6)のいずれかに変更したこと以外、実施例13と同様にして、塗布基材(2)〜(6)を得た後、排ガス浄化触媒(2)〜(6)を得た。
<Examples 14 to 18>
Except that the exhaust gas purification catalyst slurry (c1) was changed to any one of the exhaust gas purification catalyst slurries (c2) to (c6), the coated substrates (2) to (6) were obtained in the same manner as in Example 13. After that, exhaust gas purification catalysts (2) to (6) were obtained.
<比較例10〜14>
排ガス浄化触媒用スラリー(c1)を比較用の排ガス浄化触媒用スラリー(c7)〜(c11)のいずれかに変更したこと以外、実施例13と同様にして、塗布基材(7)〜(11)を得た後、比較用の排ガス浄化触媒(7)〜(11)を得た。
<Comparative Examples 10-14>
Except that the exhaust gas purification catalyst slurry (c1) was changed to any of the comparative exhaust gas purification catalyst slurries (c7) to (c11), the coated substrates (7) to (11 ), Comparative exhaust gas purification catalysts (7) to (11) were obtained.
<スラリー粘度(初期)>
排ガス浄化触媒用スラリー(c1)〜(c11)について、レオメーターPhysica MCR301(Anton Paar社製)を用いて、剪断速度4s−1で粘度(α、25℃)を測定し、下表に示した。
<Slurry viscosity (initial)>
Regarding the slurries (c1) to (c11) for exhaust gas purification catalyst, the viscosity (α, 25 ° C.) was measured at a shear rate of 4 s −1 using a rheometer Physica MCR301 (manufactured by Anton Paar) and shown in the table below. .
<スラリー粘度変化率(7日後)>
排ガス浄化触媒用スラリー(c1)〜(c11)について、7日間、25℃で、新東科学株式会社製攪拌機(スリーワンモーター BLh 1200)を用いて密閉下均一攪拌し続けた後、上記と同様にして、剪断速度4s−1で粘度(β、25℃)を測定し、粘度(α)に対する粘度(β)の変化率(百分率:β×100/α)を算出し、下表に示した。
<Slurry viscosity change rate (after 7 days)>
For the exhaust gas purifying catalyst slurries (c1) to (c11), after stirring for 7 days at 25 ° C., using a stirrer manufactured by Shinto Kagaku Co., Ltd. (Three-One Motor BLh 1200), the mixture was stirred and sealed in the same manner as above. The viscosity (β, 25 ° C.) was measured at a shear rate of 4 s −1 , and the change rate (percentage: β × 100 / α) of the viscosity (β) with respect to the viscosity (α) was calculated and shown in the table below.
<目詰まり率>
排ガス浄化触媒(1)〜(11)について、コージェライト製のハニカム型基材の入口端側を目視で観察し、セル(六角形の孔)が塞がれている数を数え、次式から、目詰まり率(%)を算出した。
(目詰まり率)=(塞がれたセルの数)×100/(全セル数)
<Clogging rate>
For the exhaust gas purification catalysts (1) to (11), the inlet end side of the cordierite honeycomb-type base material is visually observed, the number of cells (hexagonal holes) blocked is counted, and The clogging rate (%) was calculated.
(Clogging rate) = (Number of blocked cells) × 100 / (Total number of cells)
本発明の増粘剤(実施例1〜6)を用いた排ガス触媒用スラリー(実施例7〜12)を用いると、比較用のスラリー(比較例5〜9)を用いた場合に対して、目詰まりがなく均一に基材へ塗布できた。したがって、本発明の排ガス触媒用スラリーを用いれば、スラリーの固形分濃度を高くしなくても粘度を高くすることができ、基材へ目詰まりが少なく均一に塗布することができ、高い生産性(低コスト)で排ガス浄化触媒を調製できる。また、本発明の増粘剤(実施例1〜6)を用いると、比較用のスラリー(比較例5〜9)を用いた場合に対して、粘度変化率が著しく小さく、長期間にわたって、基材へ目詰まりが少なく均一に塗布することができ、高い生産性(低コスト)で排ガス浄化触媒を調製できる。 When the exhaust gas catalyst slurry (Examples 7 to 12) using the thickener (Examples 1 to 6) of the present invention is used, the case of using the comparative slurry (Comparative Examples 5 to 9), There was no clogging and the coating could be applied uniformly to the substrate. Therefore, if the slurry for exhaust gas catalyst of the present invention is used, the viscosity can be increased without increasing the solid content concentration of the slurry, it can be uniformly applied to the substrate with less clogging, and high productivity. An exhaust gas purification catalyst can be prepared at a low cost. Further, when the thickener of the present invention (Examples 1 to 6) is used, the rate of change in viscosity is remarkably small compared with the case of using a comparative slurry (Comparative Examples 5 to 9), The material can be uniformly coated with less clogging, and an exhaust gas purification catalyst can be prepared with high productivity (low cost).
Claims (10)
(メタ)アクリル酸(A)単位と(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位とから構成される共重合体(X)を含有してなり、
(メタ)アクリル酸(A)単位及び(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位のモル数に基づいて、(メタ)アクリル酸(A)単位の含有量が80〜97モル%、(メタ)アクリル酸アルコキシポリオキシアルキレンエステル(B)単位の含有量が3〜20モル%であり、共重合体(X)の重量平均分子量が1万〜3万であることを特徴とする増粘剤。 A thickener for increasing the viscosity of a slurry for exhaust gas purification catalyst containing a heat-resistant inorganic oxide supporting a noble metal and a dispersion medium,
Containing a copolymer (X) composed of (meth) acrylic acid (A) units and (meth) acrylic acid alkoxypolyoxyalkylene ester (B) units;
Based on the number of moles of the (meth) acrylic acid (A) unit and the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit, the content of the (meth) acrylic acid (A) unit is 80 to 97 mol%, An increase characterized in that the content of the (meth) acrylic acid alkoxypolyoxyalkylene ester (B) unit is 3 to 20 mol%, and the weight average molecular weight of the copolymer (X) is 10,000 to 30,000. Sticky.
基材に、スラリーを塗布して塗布基材を得る塗布工程(2)、
並びに塗布基材を乾燥し、焼成して排気ガス浄化触媒を得る乾燥焼成工程(3)を含むことを特徴とする排ガス浄化触媒の製造方法。 A slurrying step (1) for obtaining a slurry by uniformly mixing and dispersing the thickener according to claim 1, the heat-resistant inorganic oxide supporting a noble metal, and a dispersion medium,
Application step (2) of applying a slurry to a substrate to obtain a coated substrate,
And a method for producing an exhaust gas purification catalyst, comprising a drying and firing step (3) of drying and firing the coated substrate to obtain an exhaust gas purification catalyst.
An internal combustion engine equipped with an exhaust gas purifying catalyst manufactured by the manufacturing method according to claim 5.
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JPS59193126A (en) * | 1983-04-18 | 1984-11-01 | Kao Corp | Dispersing agent for calcium carbonate |
JPS60225653A (en) * | 1984-04-05 | 1985-11-09 | エンゲルハード・コーポレーシヨン | Impregnation method |
JP2008302304A (en) * | 2007-06-07 | 2008-12-18 | Cataler Corp | Method and apparatus for depositing noble metal |
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