JPH03243605A - Production of styrene-based copolymer - Google Patents
Production of styrene-based copolymerInfo
- Publication number
- JPH03243605A JPH03243605A JP3736090A JP3736090A JPH03243605A JP H03243605 A JPH03243605 A JP H03243605A JP 3736090 A JP3736090 A JP 3736090A JP 3736090 A JP3736090 A JP 3736090A JP H03243605 A JPH03243605 A JP H03243605A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- methacrylic acid
- weight
- component
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920001577 copolymer Polymers 0.000 title abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 50
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 claims abstract 2
- 229920006249 styrenic copolymer Polymers 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 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 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
Abstract
Description
【発明の詳細な説明】
(イ)産業上の利用分野
本発明はスチレン系共重合体の製造方法に関する。更に
詳しくは、耐熱性、透明性、強度のすぐれたスチレン系
単量体−メタクリル酸系共重合体を懸濁重合によって製
造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a method for producing a styrenic copolymer. More specifically, the present invention relates to a method for producing a styrene monomer-methacrylic acid copolymer having excellent heat resistance, transparency, and strength by suspension polymerization.
(0)従来の技術
スチレンとメタクリル酸との共重合体を得る方法として
、従来から種々の手法が提案されており、比較的透明な
スチレン−メタクリル酸共重合体が懸濁重合方法によっ
て製造可能なことは特公昭60−54983号公報及び
特開昭61−266418号公報等に開示されているよ
うに公知である。(0) Prior art Various methods have been proposed to obtain copolymers of styrene and methacrylic acid, and relatively transparent styrene-methacrylic acid copolymers can be produced by suspension polymerization. This is well known as disclosed in Japanese Patent Publication No. 60-54983 and Japanese Patent Application Laid-open No. 61-266418.
(ハ)発明が解決しようとする課題
しかしながら従来の懸濁重合条件では、メタクリル酸単
量体が水とスチレン系単量体の両方に溶解し、重合後期
に水から懸濁粒子中に吸収されることから、組成が不均
一となりやすく、耐熱性、透明性及び強度等で充分な特
性をもつ共重合体を得ることができないという課題があ
った。(c) Problems to be solved by the invention However, under conventional suspension polymerization conditions, methacrylic acid monomer dissolves in both water and styrene monomer, and is absorbed from water into suspended particles in the late stage of polymerization. Therefore, there was a problem that the composition tends to be non-uniform and it is impossible to obtain a copolymer with sufficient properties such as heat resistance, transparency, and strength.
(ニ)課題を解決するための手段及び作用そこで本発明
者は、かかる課題を解決すべく種々検討を行なった結果
、懸濁重合における組成の不均一性を解決する知見を得
、耐熱性、透明性及び強度のすくれたスチレン系単量体
−メタクリル酸系共重合体を製造する方法を完成するに
至った。(d) Means and effect for solving the problems Therefore, as a result of various studies in order to solve the problems, the present inventors obtained the knowledge to solve the compositional non-uniformity in suspension polymerization, and improved heat resistance, A method for producing a styrene monomer-methacrylic acid copolymer with low transparency and strength has been completed.
すなわち本発明は、スチレン系単量体とメタクリル酸単
量体を懸濁重合させる方法において、スチレン系単量体
とメタクリル酸単量体の全使用量の比率が、スチレン系
単量体:メタクリル酸単量体として75〜95重量%:
5〜25重量%(両者の合計は100重量%)であり、
重合開始時にスチレン系単量体をその全使用量の75〜
99重量%とメタクリル酸単量体をその全使用量の20
〜80重量%存在せしめ、重合途中に残りの単量体すな
わち全使用量の1〜25重量%のスチレン系単量体と全
使用量の20〜80重量%のメタクリル酸単量体を重合
系内に添加して共重合させることを特徴とするスチレン
系共重合体の製造方法に関する。That is, the present invention provides a method for suspension polymerizing styrene monomers and methacrylic acid monomers, in which the ratio of the total amount of styrene monomers and methacrylic acid monomers is styrene monomer:methacrylic acid monomer. 75-95% by weight as acid monomer:
5 to 25% by weight (total of both is 100% by weight),
At the start of polymerization, the styrenic monomer is added to 75 to 75% of the total amount used.
99% by weight and 20% of the total usage amount of methacrylic acid monomer
~80% by weight of the remaining monomers, i.e., 1 to 25% by weight of the total amount of styrene monomer and 20 to 80% of the total amount of methacrylic acid monomer to be added to the polymerization system. The present invention relates to a method for producing a styrenic copolymer, which is characterized in that the styrenic copolymer is added to a styrene-based copolymer and copolymerized.
以下に本発明を更に詳しく説明する。The present invention will be explained in more detail below.
本発明で使用するスチレン系単量体としては、スチレン
、α−メチルスチレン、ビニルトルエン、ターシャリ−
ブチルトルエン等の単独またはこれらの混合物である。Examples of the styrenic monomer used in the present invention include styrene, α-methylstyrene, vinyltoluene, and tertiary styrene.
Butyltoluene, etc. alone or a mixture thereof.
本発明で使用するスチレン系単量体とメタクリル酸単量
体の比率は、スチレン系単量体;メタクリル酸単量体と
して75〜95重量%:5〜25重量%であるが、85
〜93重量%ニア〜15重量%(いずれも両者の合計は
100重量%である。The ratio of the styrene monomer and methacrylic acid monomer used in the present invention is styrene monomer: 75 to 95% by weight as methacrylic acid monomer: 5 to 25% by weight, but 85
~93% by weight Near ~15% by weight (the total of both is 100% by weight).
)の比率が更に好ましい。メタクリル酸単量体が5重量
%未満であると得られる共重合体が耐熱性に劣り、25
重量%を越えると重合時の懸濁安定性が悪くなり収率の
低下等を招く。) is more preferable. If the methacrylic acid monomer content is less than 5% by weight, the resulting copolymer will have poor heat resistance,
If it exceeds % by weight, the suspension stability during polymerization will deteriorate, leading to a decrease in yield, etc.
又、本発明ではスチレン系単量体とメタクリル酸単量体
のほかにアクリロニトリル、メタクリル酸メチル等の共
重合可能な単量体を共重合させることもできる。これら
の単量体はスチレン系単量体とメタクリル酸単量体の合
計100重量部に対し10重量部以下が好ましい。これ
らの単量体は、例えば、スチレン系単量体と共に重合系
に加えることができる。Further, in the present invention, in addition to the styrene monomer and methacrylic acid monomer, copolymerizable monomers such as acrylonitrile and methyl methacrylate can also be copolymerized. The amount of these monomers is preferably 10 parts by weight or less based on the total of 100 parts by weight of the styrene monomer and methacrylic acid monomer. These monomers can be added to the polymerization system together with, for example, styrenic monomers.
本発明の製造方法においては、各単量体を分割して重合
系に加えることが特徴である。すなわち、重合開始時に
はスチレン系単量体及びメタクリル酸単量体をそれぞれ
その使用量の75〜95重量%及び5〜25重量%だけ
存在せしめ、重合を開始せしめた後、残りの単量体をそ
れぞれ重合系に添加して重合を継続させる。この重合途
中で単量体を加える時期としては、重合開始直後から重
合率80%までの間に添加することが好ましい。重合途
中で加える各単量体はそれぞれ別々に重合系内に添加し
てもよいが、それらの一部又は全部を混合したものを添
加すると、冬期における単量体の凍結を防止できる等の
点で好ましい。The production method of the present invention is characterized in that each monomer is divided and added to the polymerization system. That is, at the start of polymerization, styrene monomer and methacrylic acid monomer are present in amounts of 75 to 95% by weight and 5 to 25% by weight of the amount used, respectively, and after starting polymerization, the remaining monomers are added. Each is added to the polymerization system to continue polymerization. As for the timing of adding the monomer during this polymerization, it is preferable to add the monomer immediately after the start of the polymerization until the polymerization rate is 80%. Each monomer added during polymerization may be added separately to the polymerization system, but adding a mixture of some or all of them can prevent freezing of the monomers in winter, etc. It is preferable.
単量体を重合途中に添加する方法としては特に制限はな
く、少なくとも1回添加すればよく、断続的に数回添加
してもよく、連続的に添加しても差し支えない。There is no particular restriction on the method of adding the monomer during the polymerization, and it may be added at least once, may be added intermittently several times, or may be added continuously.
重合途中に添加するスチレン系単量体がスチレン系単量
体全量の1重置%未満であると、懸濁粒子中に吸収され
生成する共重合体中のメタクリル酸の割合が重合の後期
に高くなり、又25重量%を越えると、懸濁粒子中に吸
収され生成する共重合体中のメタクリル酸の割合が重合
の後期に低くなって、組成分布の不均一な共重合体にな
る為、得られる共重合体の耐熱性、透明性及び強度が損
なわれる。又、重合途中に添加するメタクリル酸単量体
がメタクリル酸単量体全量の20重量%未満であると、
重合の前期に生成する共重合体中のメタクリル酸含有量
が多くなり、また80重量%を越えると、重合の前期に
生成する共重合体中のメタクリル酸含有量が少なくなっ
て、組成分布の不均一な共重合体になる為、得られる共
重合体の耐熱性、透明性及び強度が損なわれる。If the styrenic monomer added during the polymerization is less than 1% by weight of the total amount of styrenic monomers, the proportion of methacrylic acid in the copolymer that is absorbed into the suspended particles and formed will decrease in the late stage of the polymerization. If it exceeds 25% by weight, the proportion of methacrylic acid in the copolymer that is absorbed into the suspended particles and formed becomes low in the later stages of polymerization, resulting in a copolymer with an uneven composition distribution. , the heat resistance, transparency and strength of the resulting copolymer are impaired. In addition, when the methacrylic acid monomer added during polymerization is less than 20% by weight of the total amount of methacrylic acid monomer,
The methacrylic acid content in the copolymer produced in the first stage of polymerization increases, and if it exceeds 80% by weight, the methacrylic acid content in the copolymer produced in the first stage of polymerization decreases, causing a change in the composition distribution. Since the copolymer is non-uniform, the heat resistance, transparency and strength of the resulting copolymer are impaired.
本発明における懸濁重合には、例えば第三リン酸カルシ
ウムやポリビニルアルコール等の公知の分散剤が使用で
きる。その使用量は水に対して0.01〜0.5重量%
が適している。For the suspension polymerization in the present invention, known dispersants such as tribasic calcium phosphate and polyvinyl alcohol can be used. The amount used is 0.01 to 0.5% by weight based on water.
is suitable.
重合開始剤は、例えばペンゾイルパーオキサイド、ター
ノヤリーブチルバーオキシベンヅエート等の公知の有機
過酸化物、アゾビスイソブチロニトリル等のアゾ化合物
等が使用できる。重合開始剤の使用量は単量体全量に対
して0.01〜0.5重量%が適している。As the polymerization initiator, for example, known organic peroxides such as penzoyl peroxide and ternoyarybutyl peroxybenzoate, and azo compounds such as azobisisobutyronitrile can be used. The appropriate amount of the polymerization initiator to be used is 0.01 to 0.5% by weight based on the total amount of monomers.
重合温度は、重合開始剤の10時間半減期温度から30
分半減期温度の間で行なうことが好ましい。The polymerization temperature is 30 minutes from the 10-hour half-life temperature of the polymerization initiator.
Preferably, it is carried out between the minute half-life temperatures.
更に必要に応して、ポリスチレンの場合と同じように、
可塑剤、滑剤、離型剤、熱安定剤、酸化防止荊等の公知
の添加剤を単量体に添加して重合することもできる。Furthermore, if necessary, as in the case of polystyrene,
Known additives such as plasticizers, lubricants, mold release agents, heat stabilizers, and antioxidants can also be added to the monomers for polymerization.
(ネ)実施例
次に実施例をあげるが、本発明はこれらの例によって制
限されるものではない。(v) Examples Examples will be given next, but the present invention is not limited to these examples.
実施例 1
容量15Lのオートクレーブに純水6kgとポリビニル
アルコール6gを加工、300 rpmに撹拌し、続い
てスチレン5.1kg、メタクリル酸3oOg及びター
シャリープチルバーオキシヘンヅエート6gを添加し、
オートクレーブ内を窒素ガスで置換してから密閉した。Example 1 6 kg of pure water and 6 g of polyvinyl alcohol were processed into an autoclave with a capacity of 15 L, stirred at 300 rpm, and then 5.1 kg of styrene, 300 g of methacrylic acid, and 6 g of tertiary butyl baroxyhendoate were added,
The inside of the autoclave was replaced with nitrogen gas and then sealed.
次いで昇温を始め110″Cで5時間重合を行なった。Next, the temperature started to increase and polymerization was carried out at 110''C for 5 hours.
この時、スチレン300gとメタクリル酸300gの混
合物を、110°Cに達したときから5時間かけて添加
を行なった。添加終了時の重合率は78.2%であった
。更に140°Cで3時間保持し重合を完結させた。次
いで重合した共重合体を常法に従って中和、脱水及び乾
燥し、押出機によりベレット形状とした。物性を表1に
示す。At this time, a mixture of 300 g of styrene and 300 g of methacrylic acid was added over 5 hours from the time the temperature reached 110°C. The polymerization rate at the end of the addition was 78.2%. The mixture was further held at 140°C for 3 hours to complete the polymerization. Next, the polymerized copolymer was neutralized, dehydrated, and dried according to a conventional method, and was formed into a pellet shape using an extruder. The physical properties are shown in Table 1.
実施例 2
オートクレーブに添加するスチレンの量を重合開始前5
.3kg、重合中100gとした以外は実施例1と同様
に行なった。添加終了時の重合率は79.5%であった
。物性を表1に示す。Example 2 The amount of styrene added to the autoclave was adjusted to 5 before the start of polymerization.
.. The same procedure as in Example 1 was carried out except that the weight was 3 kg and 100 g during polymerization. The polymerization rate at the end of the addition was 79.5%. The physical properties are shown in Table 1.
実施例 3
オートクレーブに添加するスチレンの量を重合開始前4
.4kg、重合中1000gとした以外は実施例1と同
様に行なった。添加終了時の重合率は76.8%であり
だ。物性を表1に示す。Example 3 The amount of styrene added to the autoclave was adjusted to 4 before the start of polymerization.
.. The same procedure as in Example 1 was carried out except that the weight was 4 kg and 1000 g during polymerization. The polymerization rate at the end of the addition was 76.8%. The physical properties are shown in Table 1.
実施例 4
オートクレーブに添加するメタクリル酸の量を重合開始
前150g、重合中450gとした以外は実施例1と同
様に行なった。添加終了時の重合率は77.7%であっ
た。物性を表1に示す。Example 4 The same procedure as in Example 1 was conducted except that the amount of methacrylic acid added to the autoclave was 150 g before the start of polymerization and 450 g during polymerization. The polymerization rate at the end of the addition was 77.7%. The physical properties are shown in Table 1.
実施例 5
オートクレーブに添加するメタクリル酸の量を重合開始
前450g、重合中150gとした以外は実施例1と同
様に行なった。添加終了時の重合率は79,0%であっ
た。物性を表1に示す。Example 5 The same procedure as in Example 1 was conducted except that the amount of methacrylic acid added to the autoclave was 450 g before the start of polymerization and 150 g during polymerization. The polymerization rate at the end of the addition was 79.0%. The physical properties are shown in Table 1.
比較例 1
オートクレーブに添加するスチレンの量を重合開始前5
.4kgとし、重合中には添加しないものとした以外は
実施例1と同様に行なった。物性を表1に示す。Comparative Example 1 The amount of styrene added to the autoclave was adjusted to 5 before the start of polymerization.
.. The same procedure as in Example 1 was conducted except that the weight was 4 kg and no addition was made during the polymerization. The physical properties are shown in Table 1.
比較例 2
オートクレーブに添加するスチレンの量を重合開始前4
.0kgとし、重合中1.4kgとした以外は実施例1
と同様に行なった。添加終了時の重合率は69.8%で
あった。物性を表1に示す。Comparative Example 2 The amount of styrene added to the autoclave was changed to 4 before the start of polymerization.
.. Example 1 except that the weight was 0 kg and the weight was 1.4 kg during polymerization.
I did the same thing. The polymerization rate at the end of the addition was 69.8%. The physical properties are shown in Table 1.
比較例 3
オートクレーブに添加するメタクリル酸の量を重合開始
前にはゼロ(無添加)、重合中600gとした以外は実
施例1と同様に行なった。添加終了時の重合率は75.
6%であった。物性を表1に示す。Comparative Example 3 The same procedure as in Example 1 was conducted except that the amount of methacrylic acid added to the autoclave was zero (no addition) before the start of polymerization and 600 g during polymerization. The polymerization rate at the end of the addition was 75.
It was 6%. The physical properties are shown in Table 1.
比較例 4
オートクレーブに添加するメタクリル酸の量を重合開始
前600g、重合中には添加しないものとした以外は実
施例1と同様に行なった。添加終了時の重合率は80.
3%であった。物性を表1に示す。Comparative Example 4 The same procedure as in Example 1 was carried out except that the amount of methacrylic acid added to the autoclave was 600 g before the start of polymerization and was not added during polymerization. The polymerization rate at the end of addition was 80.
It was 3%. The physical properties are shown in Table 1.
(へ)発明の効果
本発明の製造方法によれば、耐熱性、透明性及び強度に
優れたスチレン系単量体−メタクリル酸系共重合体を効
率よく得ることが出来、工業上きわめて有用である。(F) Effects of the Invention According to the production method of the present invention, a styrene monomer-methacrylic acid copolymer having excellent heat resistance, transparency, and strength can be efficiently obtained, and is extremely useful industrially. be.
Claims (1)
る方法において、スチレン系単量体とメタクリル酸単量
体の全使用量の比率が、スチレン系単量体:メタクリル
酸単量体として75〜95重量%:5〜25重量%(両
者の合計は100重量%)であり、重合開始時にスチレ
ン系単量体をその全使用量の75〜99重量%とメタク
リル酸単量体をその全使用量の20〜80重量%存在せ
しめ、重合途中に残りの単量体すなわち全使用量の1〜
25重量%のスチレン系単量体と全使用量の20〜80
重量%のメタクリル酸単量体を重合系内に添加して共重
合させることを特徴とするスチレン系共重合体の製造方
法。In the method of suspension polymerizing styrene monomers and methacrylic acid monomers, the ratio of the total amount of styrene monomers and methacrylic acid monomers used is 75-95% by weight: 5-25% by weight (total of both is 100% by weight), and at the start of polymerization, the styrene monomer is 75-99% by weight of the total amount used, and the methacrylic acid monomer is The remaining monomer, i.e. 1 to 80% by weight of the total amount used, is added during polymerization.
25% by weight of styrenic monomer and 20-80% of the total amount used
1. A method for producing a styrenic copolymer, which comprises adding methacrylic acid monomer to a polymerization system in an amount of % by weight for copolymerization.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP3736090A JP2859915B2 (en) | 1990-02-20 | 1990-02-20 | Method for producing styrenic copolymer |
Applications Claiming Priority (1)
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JP3736090A JP2859915B2 (en) | 1990-02-20 | 1990-02-20 | Method for producing styrenic copolymer |
Publications (2)
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JPH03243605A true JPH03243605A (en) | 1991-10-30 |
JP2859915B2 JP2859915B2 (en) | 1999-02-24 |
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JP3736090A Expired - Fee Related JP2859915B2 (en) | 1990-02-20 | 1990-02-20 | Method for producing styrenic copolymer |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009256398A (en) * | 2008-04-11 | 2009-11-05 | Kao Corp | Method for producing polymer for dispersing pigment |
-
1990
- 1990-02-20 JP JP3736090A patent/JP2859915B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009256398A (en) * | 2008-04-11 | 2009-11-05 | Kao Corp | Method for producing polymer for dispersing pigment |
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JP2859915B2 (en) | 1999-02-24 |
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