JPH0493308A - Production of rubber-modified styrene resin - Google Patents
Production of rubber-modified styrene resinInfo
- Publication number
- JPH0493308A JPH0493308A JP21116290A JP21116290A JPH0493308A JP H0493308 A JPH0493308 A JP H0493308A JP 21116290 A JP21116290 A JP 21116290A JP 21116290 A JP21116290 A JP 21116290A JP H0493308 A JPH0493308 A JP H0493308A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- weight
- rubber
- monomer
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 229920005989 resin Polymers 0.000 title abstract description 6
- 239000011347 resin Substances 0.000 title abstract description 6
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000000539 dimer Substances 0.000 claims abstract description 11
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 229920001890 Novodur Polymers 0.000 claims description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229920002857 polybutadiene Polymers 0.000 abstract description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003440 styrenes Chemical class 0.000 abstract description 3
- 239000005062 Polybutadiene Substances 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000003756 stirring Methods 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
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 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 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical class CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、熱溶融時の流動特性、即ち成形性に優れた、
例えば、食品容器、OA機器、家電製品等に好適なゴム
変性スチレン系樹脂の製造方法に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides a method for producing a material having excellent flow characteristics during hot melting, that is, excellent moldability.
For example, the present invention relates to a method for producing rubber-modified styrenic resin suitable for food containers, OA equipment, home appliances, etc.
ゴム変性スチレン系樹脂の流動性を改良する方法として
、従来から多くの方法か提案されている。Many methods have been proposed to improve the fluidity of rubber-modified styrenic resins.
例えば、特開昭29−7892号公報にはミネラルオイ
ルの添加による方法が開示されている。しかしこの方法
では必要な流動性を得るために多量の添加が必要であり
、このため耐熱性および機械的強度の低下か著しく好ま
しくない。また、特公昭481236号公報には、高級
脂肪酸もしくはその金属塩を添加する方法が開示されて
いる。しかしこの方法では金型からの離型性は改良され
るが、流動性に関しては顕著な効果を得るに至っていな
い。さらに、スチレン系樹脂連続相の分子量を下げるこ
とにより流動性を改良する方法が公知である。この方法
は、連鎖移動剤として慣用されているメルカプタン類の
添加量を増加する手法である。しかしながら、高流動性
を達成すべく、メルカプタン類を多量に添加すると、耐
衝撃性の低下および異臭の問題を生ずるため、添加量を
制限しているのが実情である。For example, JP-A-29-7892 discloses a method using mineral oil addition. However, this method requires the addition of a large amount in order to obtain the necessary fluidity, which is undesirable as it significantly reduces heat resistance and mechanical strength. Further, Japanese Patent Publication No. 481236 discloses a method of adding higher fatty acids or metal salts thereof. However, although this method improves the releasability from the mold, it has not achieved a significant effect on fluidity. Furthermore, a method of improving fluidity by lowering the molecular weight of the styrenic resin continuous phase is known. This method involves increasing the amount of mercaptans commonly used as chain transfer agents. However, in order to achieve high fluidity, adding a large amount of mercaptans causes problems such as a decrease in impact resistance and an off-odor, so the amount of mercaptans added is actually limited.
本発明はこの様な従来の技術の欠点を克服し、優れた流
動特性を有し、かつ諸用途に対応可能なゴム変性スチレ
ン系樹脂を提供することを目的としてなされたものであ
る。The present invention has been made with the object of overcoming the drawbacks of such conventional techniques and providing a rubber-modified styrenic resin that has excellent flow characteristics and can be used for various purposes.
本発明者らは、メルカプタン類に替えて、α−メチルス
チレンの不飽和二量体を添加して高流動化を試みた。し
かしながら高流動性を得るためには、かなりの量を必要
とし、異臭は無いもの\、耐熱性か大幅に低下して不都
合であった。The present inventors attempted to achieve high fluidity by adding an unsaturated dimer of α-methylstyrene instead of mercaptans. However, in order to obtain high fluidity, a considerable amount is required, and although there is no off-odor, the heat resistance is significantly reduced, which is disadvantageous.
さらに、鋭意研究を重ねた結果、α−メチルスチレンの
不飽和二量体とメルカプタン類とを併用することによっ
て異臭が殆んど無く、物性バランスのとれた、かつ流動
特性に優れたゴム変性スチレン系樹脂か得られることを
見比し、本発明を完成するに至った。Furthermore, as a result of extensive research, we have found that by using an unsaturated dimer of α-methylstyrene in combination with mercaptans, we have created a rubber-modified styrene that has virtually no off-odor, has well-balanced physical properties, and has excellent fluidity. The present invention was completed based on the fact that a system resin could be obtained.
すなわち、本発明は、ブタジェン系ゴム状重合体の存在
下で、スチレン系単量体を重合させてゴム変性スチレン
系樹脂を製造する方法において、(a) 前記ゴム状
重合体の含有量か3〜IO重量%であり、
(b) 前記スチレン系単量体100虫量部当り、α
−メチルスチレンの不飽和二量体0.2〜0.5重量部
を重合開始前に添加し、かつ
(c) スチレン系単量体の重合率か2〜lO重量%
の範囲内て前記スチレン系単量体100重量部当り、メ
ルカプタン類0.001〜0.05重量部を添加するこ
とを特徴とするゴム変性スチレン系樹脂の製造方法を提
供しようとするものである。That is, the present invention provides a method for producing a rubber-modified styrenic resin by polymerizing a styrenic monomer in the presence of a butadiene rubbery polymer, comprising: (a) a content of the rubbery polymer; ~IO weight%, (b) per 100 parts of the styrenic monomer, α
- 0.2 to 0.5 parts by weight of an unsaturated dimer of methylstyrene is added before the start of polymerization, and (c) the polymerization rate of the styrenic monomer is 2 to 10% by weight.
It is an object of the present invention to provide a method for producing a rubber-modified styrenic resin, characterized in that 0.001 to 0.05 parts by weight of mercaptans are added per 100 parts by weight of the styrenic monomer within the range of .
以下本発明の内容について詳しく説明する。The contents of the present invention will be explained in detail below.
本発明におけるスチレン系単量体は、スチレン単独また
はスチレンと共重合可能な単量体との混合物であり、ス
チレンと共重合可能な単量体としては、例えばα−メチ
ルスチレン、ビニルトルエン等の芳香族モノビニル化合
物、アクリロニトリル、メタアクリル酸メチル、アクリ
ル酸メチル、メタアクリル酸、アクリル酸、無水マレイ
ン酸、フェニルマレイミド等が用いられる。これらの単
量体は1種用いてもよいし、2種以上を組み合わせて用
いてもよいが、通常60重量%以下の割合で用いられる
。The styrenic monomer in the present invention is styrene alone or a mixture of monomers copolymerizable with styrene. Examples of monomers copolymerizable with styrene include α-methylstyrene, vinyltoluene, etc. Aromatic monovinyl compounds, acrylonitrile, methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, maleic anhydride, phenylmaleimide, and the like are used. These monomers may be used alone or in combination of two or more, but are usually used in a proportion of 60% by weight or less.
一方、ジエン系ゴム状重合体としてはポリブタジェン、
スチレン−ブタジェン共重合体等が用いられる。On the other hand, diene-based rubbery polymers include polybutadiene,
A styrene-butadiene copolymer or the like is used.
本発明のゴム変性スチレン系樹脂においては、前記ゴム
状重合体を3〜10重量%の割合で含有することが必要
である。前記ゴム状重合体の含有量が3重量%未満では
、耐衝撃性の改良が十分でなく、10重量%を超えると
引張り強さが低下し好ましくない。The rubber-modified styrenic resin of the present invention needs to contain the rubbery polymer in a proportion of 3 to 10% by weight. If the content of the rubbery polymer is less than 3% by weight, the impact resistance will not be improved sufficiently, and if it exceeds 10% by weight, the tensile strength will decrease, which is not preferable.
本発明に用いるa−メチルスチレンの不飽和二量体は、
2,4ジフェニル−4−メチル−1−ペンテンを主成分
(含有量94%以上)とした市販の連鎖移動剤を用いる
ことができる。前記不飽和二量体は、スチレン系単量体
100重量部当り0.2〜0.5重量部を重合開始前に
添加することが必要である。前記不飽和二量体が02重
量部未満では、流動性の改善か充分でなく、一方、0.
5重量%を超えると耐衝撃性の低下か著しく好ましくな
い。The unsaturated dimer of a-methylstyrene used in the present invention is
A commercially available chain transfer agent containing 2,4 diphenyl-4-methyl-1-pentene as a main component (content of 94% or more) can be used. The unsaturated dimer needs to be added in an amount of 0.2 to 0.5 parts by weight per 100 parts by weight of the styrenic monomer before the start of polymerization. If the amount of the unsaturated dimer is less than 0.2 parts by weight, the fluidity will not be improved sufficiently;
If it exceeds 5% by weight, the impact resistance will be significantly lowered, which is undesirable.
また、本発明に用いるメルカプタン類としては、例えば
n−ドデシルメルカプタン、t−ドデシルメルカプタン
などを挙げることができる。前記メルカプタン類は、ス
チレン系単量体の重合率が2〜10重量%の範囲内で、
スチレン系単量体100重口部肖り0.001〜0.0
5重量部添加することか必要である。前記重合率が2重
量%未満では、流動性の低下か著しく、10重量%を超
えると耐衝撃性の低下が見られ好ましくない。Examples of the mercaptans used in the present invention include n-dodecylmercaptan and t-dodecylmercaptan. The mercaptans have a polymerization rate of styrenic monomer in the range of 2 to 10% by weight,
Styrenic monomer 100% weight 0.001-0.0
It is necessary to add 5 parts by weight. When the polymerization rate is less than 2% by weight, the fluidity is significantly lowered, and when it exceeds 10% by weight, the impact resistance is undesirably lowered.
一方、前記メルカプタン類の添加量か0.001重量%
未満では、添加による改良効果が少なく、0.05重量
%を超えると異臭が感じられるようになり好ましくない
。On the other hand, the amount of the mercaptans added is 0.001% by weight.
If it is less than 0.05% by weight, an unpleasant odor may be felt, which is not preferable.
本発明の方法を用いて、流動性に優れたゴム変性スチレ
ン系樹脂を製造するプロセスについては特に限定するも
のではないが、塊状−懸濁重合法、塊状重合法か好適に
用いられる。The process for producing a rubber-modified styrenic resin with excellent fluidity using the method of the present invention is not particularly limited, but a bulk-suspension polymerization method or a bulk polymerization method is preferably used.
一例として塊状−懸濁重合法について説明する。A bulk-suspension polymerization method will be explained as an example.
ゴム状重合体をスチレン単量体またはスチレン単量体と
、スチレン単量体と共重合可能な前記単量体の混合物に
溶解し、α−メチルスチレンの不飽和二量体を所定量添
加し、必要あれば重合開始剤を加え、撹拌下に100−
150℃に加温し重合を行なう。重合率か2〜10重量
%の範囲内で必要量のメルカプタンを添加し、更に重合
率15〜50重量%になるまで重合を行う。A rubbery polymer is dissolved in a styrene monomer or a mixture of the styrene monomer and the monomer copolymerizable with the styrene monomer, and a predetermined amount of an unsaturated dimer of α-methylstyrene is added. , add a polymerization initiator if necessary, and heat to 100% while stirring.
Polymerization is carried out by heating to 150°C. A necessary amount of mercaptan is added so that the polymerization rate is within the range of 2 to 10% by weight, and polymerization is further carried out until the polymerization rate is 15 to 50% by weight.
次に、この重合液を第三燐酸カルシウム、炭酸カルシウ
ム等の無機塩類と界面活性剤との組合せ、あるいは、ポ
リビニルアルコール等水溶性高分子を懸濁剤として水相
に懸濁し重合開始剤を加えて重合率100%近くまで重
合する。懸濁重合温度については用いる重合開始剤によ
って任意に設定できる。Next, this polymerization solution is suspended in an aqueous phase using a combination of an inorganic salt such as tricalcium phosphate or calcium carbonate and a surfactant, or a water-soluble polymer such as polyvinyl alcohol as a suspending agent, and a polymerization initiator is added. Polymerization is carried out to a polymerization rate of nearly 100%. The suspension polymerization temperature can be arbitrarily set depending on the polymerization initiator used.
重=U始剤としてはベンゾイルパーオキシド、t−ブチ
ルパーベンゾエート、ジt−プチルバーオキンド等の有
機過酸化物類あるいはアゾビスイソブチロニトリル等が
使用できる。As the heavy = U initiator, organic peroxides such as benzoyl peroxide, t-butyl perbenzoate, di-t-butyl baroquinde, azobisisobutyronitrile, etc. can be used.
このようにして得られた重合体ビーズスラリーは通常の
方法で処理して取出し、乾燥し、ベレット化することに
より本発明のゴム変性スチレン系樹脂を得ることかでき
る。The polymer bead slurry thus obtained can be treated in a conventional manner, taken out, dried, and pelletized to obtain the rubber-modified styrenic resin of the present invention.
なお、上記樹脂には通常用いられる種々の添加剤、例え
ば滑剤、可塑剤、酸化防止剤、紫外線吸収剤、難燃剤、
帯電防止剤、離型剤、着色剤等を添加することかできる
。Note that the above resin contains various additives commonly used, such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants,
Antistatic agents, mold release agents, colorants, etc. may be added.
次に、実施例によりさらに具体的に説明するが、本発明
はこれらの例によって限定されるものではない。Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.
なお、物性のIn2定は次に示す方法で行った。In addition, the In2 constant of physical properties was performed by the following method.
(1)メルト・フローレート: JIS K6871に
準拠した。(1) Melt flow rate: Based on JIS K6871.
(2〉ビカット軟化温度二 同 上
(3)アイゾツト衝撃強さ: 同 上(4)引張り
強さ二 同 上
また異臭の有無も判定した。(2) Vicat softening temperature 2 Same as above (3) Izot impact strength: Same as above (4) Tensile
Strength 2 Same as above.The presence or absence of an unusual odor was also determined.
実施例 1
容積5gの撹拌機付きオートクレーブにスチレンモノマ
ー100重量部を仕込み、ポリブタジェンゴム6重量部
、ミネラルオイル6重量部を加え溶解した。塊状重合を
開始する前に、α−メチルスチレンの不飽和二量体0.
3重量部を添加し、撹拌しながら昇温し、115℃で1
時間塊状重合を行った。この時点でのスチレンモノマー
の重合率は5重量%であった。n−ドデシルメルカプタ
ン0.01重量部を添加して更に3時間重合を継続し、
スチレンモノマーの重合率25重量%の予i重合液を得
た。Example 1 100 parts by weight of styrene monomer was charged into an autoclave having a volume of 5 g and equipped with a stirrer, and 6 parts by weight of polybutadiene rubber and 6 parts by weight of mineral oil were added and dissolved. Before starting the bulk polymerization, 0.0% of the unsaturated dimer of α-methylstyrene was added.
Add 3 parts by weight, raise the temperature while stirring, and heat to 115°C.
Time bulk polymerization was carried out. The polymerization rate of the styrene monomer at this point was 5% by weight. Adding 0.01 part by weight of n-dodecyl mercaptan and continuing polymerization for an additional 3 hours,
A pre-polymerization solution with a styrene monomer polymerization rate of 25% by weight was obtained.
次に、容1aloIの撹拌機付きオートクレーブに水1
00重量部、第三燐酸カルシウム0.5重量部、ドデシ
ルベンゼンスルフオン酸ソーダ0.001重量部を仕込
み、次に前記予備重合液100重量部、重合開始剤とし
てベンゾイルパーオキサイド0.3重皿部、t−ブチル
パーオキシベンゾエート0.2重量部を加え、90℃で
4時間、続いて140℃で2時間、撹拌下で懸濁重合を
行い、ゴム変性ポリスチレン重合体ビーズを得た。この
ビーズを単軸押出機にてペレットとし、物性測定に供し
た。第1表に測定結果を示す。Next, in an autoclave with a stirrer with a volume of 1 aloI, add 1 volume of water.
0.00 parts by weight, 0.5 parts by weight of tricalcium phosphate, and 0.001 parts by weight of sodium dodecylbenzenesulfonate, then 100 parts by weight of the prepolymerization solution, and 0.3 parts by weight of benzoyl peroxide as a polymerization initiator. and 0.2 parts by weight of t-butyl peroxybenzoate were added thereto, and suspension polymerization was carried out at 90°C for 4 hours and then at 140°C for 2 hours with stirring to obtain rubber-modified polystyrene polymer beads. The beads were made into pellets using a single screw extruder, and the pellets were subjected to physical property measurements. Table 1 shows the measurement results.
実施例2〜3、比較例1〜3
α−メチルスチレンの不飽和二量体およびn−ドデシル
メルカプタンの添加量を第1表に示す値とした以外は、
実施例1と同様にして重合を行った。得られた重合体の
物性を第1表に示す。Examples 2-3, Comparative Examples 1-3 Except that the amounts of unsaturated α-methylstyrene dimer and n-dodecylmercaptan were set to the values shown in Table 1,
Polymerization was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained polymer.
比較例4および5
n−ドデシルメルカプタンを重合開始前に第1表に示す
値を添加した以外は、実施例1と同様にして重合を行っ
た。得られた重合体の物性を第1表に示す。Comparative Examples 4 and 5 Polymerization was carried out in the same manner as in Example 1, except that n-dodecylmercaptan was added in the amount shown in Table 1 before the start of polymerization. Table 1 shows the physical properties of the obtained polymer.
比較例 6
n−ドデシルメルカプタンの添加を重合率0.5%の時
点で行った以外は、実施例1と同様にして重合を行った
。得られた重合体の物性を第1表に示す。Comparative Example 6 Polymerization was carried out in the same manner as in Example 1, except that n-dodecylmercaptan was added at a polymerization rate of 0.5%. Table 1 shows the physical properties of the obtained polymer.
比較例 7
n−ドデシルメルカプタンの添加を重合率20%の時点
で行った以外は、
実施例1と同様にして亜
合を行った。Comparative Example 7 Subpolymerization was carried out in the same manner as in Example 1, except that n-dodecylmercaptan was added at a polymerization rate of 20%.
得られた重合体の物性を第1表に示 す。The physical properties of the obtained polymer are shown in Table 1. vinegar.
/
〔発明の効果〕
本発明の方法によって得られたゴム変性スチレン系樹脂
は、流動性に優れ、その他の物性バランスも良好であり
、かつ異臭が少なく、工業的に有用である。/ [Effects of the Invention] The rubber-modified styrenic resin obtained by the method of the present invention has excellent fluidity, has a good balance of other physical properties, and has little off-odor, and is industrially useful.
出 願 人 昭 和 電 工 株 式 日本ポリスチレン工業株式会社 代 理 人Out wish Man Akira sum electric engineering KK formula Japan Polystyrene Industries Co., Ltd. teenager Reason Man
Claims (1)
体を重合させてゴム変性スチレン系樹脂を製造する方法
において、 (a)前記ゴム状重合体の含有量が3〜10重量%であ
り、 (b)前記スチレン系単量体100重量部当り、α−メ
チルスチレンの不飽和二量体0.2〜0.5重量部を重
合開始前に添加し、かつ (c)スチレン系単量体の重合率が2〜10重量%の範
囲内で前記スチレン系単量体100重量部当り、メルカ
プタン類0.001〜0.05重量部を添加することを
特徴とするゴム変性スチレン系樹脂の製造方法。[Scope of Claims] A method for producing a rubber-modified styrenic resin by polymerizing a styrenic monomer in the presence of a butadiene-based rubbery polymer, comprising: (a) a content of the rubbery polymer of 3; (b) per 100 parts by weight of the styrenic monomer, 0.2 to 0.5 parts by weight of an unsaturated dimer of α-methylstyrene is added before the start of polymerization, and ( c) mercaptans are added in an amount of 0.001 to 0.05 parts by weight per 100 parts by weight of the styrene monomer so that the polymerization rate of the styrene monomer is within the range of 2 to 10% by weight. A method for producing rubber-modified styrenic resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21116290A JPH0493308A (en) | 1990-08-09 | 1990-08-09 | Production of rubber-modified styrene resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21116290A JPH0493308A (en) | 1990-08-09 | 1990-08-09 | Production of rubber-modified styrene resin |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0493308A true JPH0493308A (en) | 1992-03-26 |
Family
ID=16601428
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21116290A Pending JPH0493308A (en) | 1990-08-09 | 1990-08-09 | Production of rubber-modified styrene resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0493308A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5521268A (en) * | 1995-03-29 | 1996-05-28 | Eastman Kodak Company | Odor reduction in toner polymers |
-
1990
- 1990-08-09 JP JP21116290A patent/JPH0493308A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5521268A (en) * | 1995-03-29 | 1996-05-28 | Eastman Kodak Company | Odor reduction in toner polymers |
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