JP5813043B2 - Production method of chloroprene rubber - Google Patents
Production method of chloroprene rubber Download PDFInfo
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- JP5813043B2 JP5813043B2 JP2013083844A JP2013083844A JP5813043B2 JP 5813043 B2 JP5813043 B2 JP 5813043B2 JP 2013083844 A JP2013083844 A JP 2013083844A JP 2013083844 A JP2013083844 A JP 2013083844A JP 5813043 B2 JP5813043 B2 JP 5813043B2
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- JP
- Japan
- Prior art keywords
- diene
- chlorobuta
- chloroprene rubber
- cis
- chloroprene
- 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.)
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- 229920001084 poly(chloroprene) Polymers 0.000 title claims description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims description 29
- PCPYTNCQOSFKGG-ONEGZZNKSA-N (1e)-1-chlorobuta-1,3-diene Chemical compound Cl\C=C\C=C PCPYTNCQOSFKGG-ONEGZZNKSA-N 0.000 claims description 28
- PCPYTNCQOSFKGG-ARJAWSKDSA-N (1z)-1-chlorobuta-1,3-diene Chemical compound Cl\C=C/C=C PCPYTNCQOSFKGG-ARJAWSKDSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 17
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 14
- LIFLRQVHKGGNSG-UHFFFAOYSA-N 2,3-dichlorobuta-1,3-diene Chemical compound ClC(=C)C(Cl)=C LIFLRQVHKGGNSG-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 6
- PCPYTNCQOSFKGG-UHFFFAOYSA-N 1-chlorobuta-1,3-diene Chemical compound ClC=CC=C PCPYTNCQOSFKGG-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 25
- 238000004073 vulcanization Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- -1 alkali metal salt Chemical class 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- 230000006835 compression Effects 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 7
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- 239000005060 rubber Substances 0.000 description 7
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- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- PDKAXHLOFWCWIH-UHFFFAOYSA-N 1,1-dichlorobuta-1,3-diene Chemical compound ClC(Cl)=CC=C PDKAXHLOFWCWIH-UHFFFAOYSA-N 0.000 description 1
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-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
- SPQMVUPFYWDFCB-UHFFFAOYSA-N 2-hydroperoxybutane Chemical compound CCC(C)OO SPQMVUPFYWDFCB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
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- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、クロロプレンゴムの製造方法に関する。より詳しくは、ワイパーブレード、ブーツ部材、ホース部材などのゴム成形体に使用されるクロロプレンゴムの製造方法に関する。 The present invention relates to a method for producing chloroprene rubber. More specifically, the present invention relates to a method for producing chloroprene rubber used for rubber moldings such as wiper blades, boot members, and hose members.
クロロプレンゴムは、耐熱性、耐候性、耐オゾン性及び耐薬品性などに優れており、一般的工業用ゴム製品、自動車用部品及び接着剤などの幅広い分野で使用されている。このようなクロロプレンゴム成形品は、一般に、クロロプレンゴムに、加硫剤、加硫促進剤及び充填剤などを配合したクロロプレンゴム組成物を、所定形状に成形した後、加硫することにより、製造される。 Chloroprene rubber is excellent in heat resistance, weather resistance, ozone resistance and chemical resistance and is used in a wide range of fields such as general industrial rubber products, automotive parts and adhesives. Such a chloroprene rubber molded product is generally produced by molding a chloroprene rubber composition in which a vulcanizing agent, a vulcanization accelerator and a filler are blended into chloroprene rubber into a predetermined shape, followed by vulcanization. Is done.
一方、クロロプレンゴムには、低温特性、特に、低温下での圧縮永久歪や動的特性が劣るという問題点がある。そこで、従来、特定の軟化剤を配合することにより、耐低温性向上を図ったクロロプレンゴム組成物が提案されている(例えば、特許文献1〜3参照。)。 On the other hand, chloroprene rubber has a problem that low temperature characteristics, particularly compression set at low temperatures and dynamic characteristics are inferior. In view of this, conventionally, a chloroprene rubber composition has been proposed in which a specific softening agent is blended to improve low-temperature resistance (see, for example, Patent Documents 1 to 3).
しかしながら、前述した従来の技術は、配合技術による改良手法であり、この方法の場合、更なる低温特性向上のために、軟化剤の添加量を増加すると、成形時に軟化剤が表面からブリードし、クロロプレンゴム組成物と金型との接着性を低下させる原因となる。このため、配合組成ではなく、クロロプレンゴム(ポリマー)自体の低温特性改善が求められている。 However, the above-mentioned conventional technique is an improved technique based on the blending technique. In this method, when the amount of the softener added is increased to further improve the low-temperature characteristics, the softener bleeds from the surface during molding, This causes a decrease in the adhesion between the chloroprene rubber composition and the mold. For this reason, improvement of the low temperature characteristics of chloroprene rubber (polymer) itself is required instead of the compounding composition.
そこで、本発明は、低温特性が優れたクロロプレンゴムが得られるクロロプレンゴムの製造方法を提供することを主目的とする。 Then, this invention makes it the main objective to provide the manufacturing method of the chloroprene rubber from which the chloroprene rubber excellent in the low temperature characteristic is obtained.
本発明者は、前述した課題を解決するために、クロロプレンゴムの低温特性に影響を与える原料モノマー中の1−クロロブタ−1,3−ジエンについて、鋭意実験検討を行った結果、以下に示す知見を得た。1−クロロブタ−1,3−ジエンには、ap配座trans−1−クロロブタ−1,3−ジエン、cis−1−クロロブタ−1,3−ジエン及びその他の異性体が存在する。そして、これらの異性体の中でも、特に、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンが、クロロプレンゴムの耐結晶性を改善し、低温特性を向上させる効果が高いことを見出し、本発明に至った。 In order to solve the above-mentioned problems, the present inventor has conducted extensive experimental studies on 1-chlorobuta-1,3-diene in a raw material monomer that affects the low temperature characteristics of chloroprene rubber. Got. 1-Chlorobuta-1,3-diene includes ap conformation trans-1-chlorobuta-1,3-diene, cis-1-chlorobuta-1,3-diene and other isomers. Among these isomers, in particular, ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene improve the crystal resistance of chloroprene rubber, The inventors have found that the effect of improving the low temperature characteristics is high, and have reached the present invention.
即ち、本発明は、クロロプレンと、ap配座型trans−1−クロロブタ−1,3−ジエンと、cis−1−クロロブタ−1,3−ジエンと、2,3−ジクロロブタ−1,3−ジエン:2.0〜20質量%とを少なくとも含有する原料モノマーを乳化重合する工程を有し、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンのうち少なくとも一方の含有量が異なる複数のクロロプレンを混合することにより、前記原料モノマー中のap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンの総含有量を調整するクロロプレンゴムの製造方法である。
前記原料モノマー中のap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンの総含有量の調整には、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンのうち少なくとも一方を別途添加してもよい。
本発明のクロロプレンゴムの製造方法では、前記原料モノマー中のap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンの総含有量を0.5〜5質量%の範囲に調整することが好ましい。
That is, the present invention relates to chloroprene, ap conformation type trans-1-chlorobuta-1,3-diene, cis-1-chlorobuta-1,3-diene, 2,3-dichlorobuta-1,3- A process of emulsion polymerization of a raw material monomer containing at least 2.0 to 20% by weight of a diene, ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3 -By mixing a plurality of chloroprenes having different contents of at least one of the dienes, ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3 in the raw material monomer -A chloroprene rubber production method for adjusting the total content of dienes.
To adjust the total content of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene in the raw material monomer, ap conformation type trans-1-chlorobuta At least one of -1,3-diene and cis-1-chlorobuta-1,3-diene may be added separately.
In the method for producing chloroprene rubber according to the present invention, the total content of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene in the raw material monomer is 0.5. It is preferable to adjust to the range of ˜5 mass%.
本発明によれば、加硫物や成形体としたときに、従来よりも優れた低温特性が得られるクロロプレンゴムを製造することができる。 According to the present invention, when a vulcanized product or a molded body is obtained, a chloroprene rubber that can obtain low temperature characteristics superior to those of conventional ones can be produced.
以下、本発明を実施するための形態について、詳細に説明する。なお、本発明は、以下に説明する実施形態に限定されるものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below.
(第1の実施形態)
先ず、本発明の第1の実施形態に係るクロロプレンゴムについて説明する。本実施形態のクロロプレンゴムは、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンを合計で0.5質量%以上含有すると共に、2,3−ジクロロブタ−1,3−ジエンを2.0質量%以上含有する原料モノマーを乳化重合することにより得られる。
(First embodiment)
First, the chloroprene rubber according to the first embodiment of the present invention will be described. The chloroprene rubber of this embodiment contains ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene in total of 0.5% by mass or more, It is obtained by emulsion polymerization of a raw material monomer containing 2.0% by mass or more of 3-dichlorobuta-1,3-diene.
なお、原料モノマーの残部(主成分)は、主に2−クロロ−1,3−ブタジエン(以下、クロロプレンと記す。)であるが、スチレン及びその誘導体、アクリロニトリル及びメタクリレートなどのクロロプレンと重合可能な他の単量体が含まれていてもよい。 The remainder (main component) of the raw material monomer is mainly 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene), but is polymerizable with chloroprene such as styrene and its derivatives, acrylonitrile and methacrylate. Other monomers may be included.
[1−クロロブタ−1,3−ジエン:0.5質量%以上]
下記化学式1に示すap配座型trans−1−クロロブタ−1,3−ジエン、及び下記化学式2に示すcis−1−クロロブタ−1,3−ジエンは、例えばアセチレン法によりクロロプレンを製造する際に副生成物として得られる。そして、クロロプレンと共に重合すると、加硫後の低温特性が向上する。
[1-Chlorobuta-1,3-diene: 0.5% by mass or more]
The ap conformation type trans-1-chlorobuta-1,3-diene represented by the following chemical formula 1 and the cis-1-chlorobuta-1,3-diene represented by the following chemical formula 2 are used when, for example, chloroprene is produced by the acetylene method. Obtained as a by-product. And when it superposes | polymerizes with chloroprene, the low temperature characteristic after vulcanization will improve.
しかしながら、モノマー中の含有量が、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンの合計で0.5質量%未満の場合、低温特性が低下する。具体的には、低温下における永久圧縮歪みが低下する。 However, when the content in the monomer is less than 0.5 mass% in total of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene, the low temperature characteristics Decreases. Specifically, the permanent compression distortion at a low temperature decreases.
なお、原料モノマーにおけるap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンの含有量の上限値は、特に限定されるものではないが、加工安全性の観点から、5質量%以下とすることが望ましい。なお、ここでいう「加工安全性」とは、成形中に加硫して成形不良が発生しないように、加硫するまでに十分な時間が確保されているという意味であり、一般的にはスコーチタイムと関係される概念である。 In addition, the upper limit of the content of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene in the raw material monomer is not particularly limited. From the viewpoint of safety, it is desirable to be 5% by mass or less. As used herein, “processing safety” means that sufficient time is secured before vulcanization so as not to cause molding defects due to vulcanization during molding. It is a concept related to scorch time.
[2,3−ジクロロブタ−1,3−ジエン:2.0質量%以上]
2,3−ジクロロブタ−1,3−ジエンは、クロロプレンゴムの結晶性を不規則化させ、加硫後の低温特性を向上させる効果がある。しかしながら、その含有量がモノマー全量あたり2.0質量%未満の場合、十分な改善効果が得られない。そこで、本実施形態のクロロプレンゴムでは、原料モノマー中の2,3−ジクロロブタ−1,3−ジエン含有量を2.0質量%以上としている。
[2,3-dichlorobuta-1,3-diene: 2.0% by mass or more]
2,3-Dichlorobuta-1,3-diene has the effect of making the crystallinity of chloroprene rubber irregular and improving the low temperature characteristics after vulcanization. However, when the content is less than 2.0% by mass based on the total amount of monomers, a sufficient improvement effect cannot be obtained. Therefore, in the chloroprene rubber of the present embodiment, the content of 2,3-dichlorobuta-1,3-diene in the raw material monomer is 2.0% by mass or more.
一方、原料モノマーにおける2,3−ジクロロブタ−1,3−ジエン含有量の上限値は、特に限定されるものではないが、多量に添加すると脆化温度が上昇したり、機械的強度が低下したりするため、モノマー全量あたり20質量%以下に抑えることが望ましい。 On the other hand, the upper limit of the 2,3-dichlorobuta-1,3-diene content in the raw material monomer is not particularly limited, but when added in a large amount, the embrittlement temperature increases or the mechanical strength decreases. Therefore, it is desirable to keep the amount to 20% by mass or less based on the total amount of monomers.
[製造方法]
次に、本実施形態のクロロプレンゴムの製造方法について説明する。本実施形態のクロロプレンゴムの製造方法では、クロロプレンを主成分とする原料モノマーを、乳化重合する。その際、原料モノマーのap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエン含有量を合計で0.5質量%以上とし、2,3−ジクロロブタ−1,3−ジエン含有量を2.0質量%以上とする。
[Production method]
Next, the manufacturing method of the chloroprene rubber of this embodiment is demonstrated. In the method for producing a chloroprene rubber according to this embodiment, a raw material monomer containing chloroprene as a main component is emulsion-polymerized. In that case, the content of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene in the raw material monomer is 0.5% by mass or more in total, The dichlorobuta-1,3-diene content is 2.0% by mass or more.
ここで、原料モノマーにおけるap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエン含有量を合計で0.5質量%以上とする方法は、特に限定されるものではないが、例えば、ap配座型trans−1−クロロブタ−1,3−ジエン含有量及びcis−1−クロロブタ−1,3−ジエン含有量が異なるクロロプレンを用意し、それらを適宜混合して使用する方法がある。また、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンを、他の異性体から分離し、原料モノマーに直接添加してもよい。 Here, the method of setting the ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene content in the raw material monomer to 0.5% by mass or more in particular, Although not limited, for example, chloroprene having different ap conformation type trans-1-chlorobuta-1,3-diene content and cis-1-chlorobuta-1,3-diene content is prepared, There is a method of appropriately mixing and using. Moreover, ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene may be separated from other isomers and added directly to the raw material monomer.
なお、これら2,3−ジクロロブタ−1,3−ジエン、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンは、一度に全量を添加してもよいが、複数回に分割して添加することもできる。分割添加の方法は、特に限定されるものではないが、例えば、所定量を重合開始時に配合し、クロロプレンの転化率が特定の範囲の間に、残りを、一度に又は複数回に分けて、添加する方法がある。 These 2,3-dichlorobuta-1,3-diene, ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene are added all at once. However, it may be added in several divided portions. The method of divided addition is not particularly limited, but, for example, a predetermined amount is blended at the start of polymerization, the conversion rate of chloroprene is within a specific range, and the remainder is divided at once or multiple times, There is a method of adding.
また、乳化重合に使用する乳化/分散剤としては、通常のロジン酸のアルカリ金属塩を用いることができる。特に、着色安定性の観点から、不均化ロジン酸のナトリウム及び/又はカリウム塩を使用することが好ましい。 Moreover, as an emulsifier / dispersant used for emulsion polymerization, a normal alkali metal salt of rosin acid can be used. In particular, it is preferable to use sodium and / or potassium salt of disproportionated rosin acid from the viewpoint of coloring stability.
更に、本発明の効果を損なわない範囲で、乳化/分散剤として、ロジン酸のアルカリ金属塩以外の他の構造を有するものを併用することもできる。ロジン酸のアルカリ金属塩と併用可能な乳化/分散剤としては、カルボン酸型、スルホン酸型、硫酸エステル型などがあり、例えば、炭素数が8〜20個のアルキルスルホネート、アルキルアリルスルホネート、ナルタリンスルホン酸ナトリウムとホルムアルデヒドの縮合物、ポリオキシエチレンアシルエーテル、ポリオキシエチレンアルキルフェノール、ソルビタン脂肪酸エステル、ポリオキシエチレンアシルエステルなどが挙げられるが、これらに限定されるものではない。 Furthermore, as long as the effect of this invention is not impaired, what has structures other than the alkali metal salt of rosin acid can also be used together as an emulsifier / dispersant. Examples of emulsifying / dispersing agents that can be used in combination with alkali metal salts of rosin acid include carboxylic acid type, sulfonic acid type, and sulfuric acid ester type. For example, alkyl sulfonate, alkyl allyl sulfonate, null Examples include, but are not limited to, a condensate of sodium talinsulfonate and formaldehyde, polyoxyethylene acyl ether, polyoxyethylene alkylphenol, sorbitan fatty acid ester, polyoxyethylene acyl ester, and the like.
乳化重合に使用する重合開始剤は、特に限定されるものではなく、通常のクロロプレンの乳化重合に使用されるものを使用することができる。具体的には、過硫酸カリウムなどの過硫酸塩、第3−ブチルヒドロパーオキサイドなどの有機過酸化物などが好適に用いられる。 The polymerization initiator used for emulsion polymerization is not particularly limited, and those used for usual emulsion polymerization of chloroprene can be used. Specifically, persulfates such as potassium persulfate, organic peroxides such as 3-butyl hydroperoxide, and the like are preferably used.
連鎖移動剤も、特に限定されるものではなく、通常のクロロプレンの乳化重合に使用されるものが使用できる。具体的には、n−ドデシルメルカプタンやtert−ドデシルメルカプタンなどの長鎖アルキルメルカプタン類、ジイソプロピルキサントゲンジスルフィドやジエチルキサントゲンジスルフィドなどのジアルキルキサントゲンジスルフィド類、ヨードホルムなどの公知の連鎖移動剤を使用することができる。 The chain transfer agent is not particularly limited, and those used for usual emulsion polymerization of chloroprene can be used. Specifically, long chain alkyl mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan, dialkyl xanthogen disulfides such as diisopropylxanthogen disulfide and diethylxanthogen disulfide, and known chain transfer agents such as iodoform can be used. .
一方、クロロプレンラテックスの重合温度は、特に限定されるものではなく、一般に乳化重合が行われる範囲とすることができるが、低温特性改善及び生産性の観点から、重合温度は33〜58℃が好適である。 On the other hand, the polymerization temperature of the chloroprene latex is not particularly limited and can generally be within a range where emulsion polymerization is performed. However, from the viewpoint of improving low-temperature characteristics and productivity, the polymerization temperature is preferably 33 to 58 ° C. It is.
重合を停止する際に添加する重合停止剤は、特に限定されるものではなく、通常用いられているものを使用することができる。具体的には、フェノチアジン、パラ−t−ブチルカテコール、ハイドロキノン、ハイドロキノンモノメチルエーテル、ジエチルヒドロキシルアミンなどを用いることができる。前述した重合工程で得られクロロプレン重合体(クロロプレンゴム)の最終重合率は、特に限定するものではなく、0〜100%の範囲内で任意に調節することができる。ただし、生産性を考慮すると、クロロプレン重合体の最終重合率は、30%以上とすることが好ましい。 The polymerization terminator added when the polymerization is terminated is not particularly limited, and those usually used can be used. Specifically, phenothiazine, para-t-butylcatechol, hydroquinone, hydroquinone monomethyl ether, diethylhydroxylamine and the like can be used. The final polymerization rate of the chloroprene polymer (chloroprene rubber) obtained in the polymerization step described above is not particularly limited, and can be arbitrarily adjusted within a range of 0 to 100%. However, in consideration of productivity, the final polymerization rate of the chloroprene polymer is preferably 30% or more.
次に、重合工程により得られた重合液から、未反応単量体の除去(脱モノマー)を行う。その方法は、特に限定されるものではなく、減圧加熱などの公知の方法を適用することができる。 Next, the unreacted monomer is removed (demonomer) from the polymerization solution obtained in the polymerization step. The method is not particularly limited, and a known method such as heating under reduced pressure can be applied.
以上詳述したように、本実施形態のクロロプレンゴムでは、原料モノマーに2,3−ジクロロブタ−1,3−ジエンを2.0質量%以上配合しているため、結晶性を改善することができる。また、原料モノマーにおけるap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンの含有量を0.5質量%以上にしているため、効率的にかつ安定して、低温特性を向上させることができる。その結果、安定して優れた低温特性を発揮するクロロプレンゴムが得られる。 As described above in detail, in the chloroprene rubber of this embodiment, since 2.0 mass% or more of 2,3-dichlorobuta-1,3-diene is blended in the raw material monomer, the crystallinity can be improved. it can. Moreover, since the content of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene in the raw material monomer is 0.5% by mass or more, it is efficient. In addition, the low temperature characteristics can be improved stably. As a result, a chloroprene rubber that stably exhibits excellent low-temperature characteristics can be obtained.
(第2の実施形態)
次に、本発明の第2の実施形態に係るクロロプレンゴム組成物について説明する。本実施形態のクロロプレンゴム組成物は、前述したクロロプレンゴムに、加硫剤、加硫促進剤、充填剤、補強剤、軟化剤、可塑剤、滑剤、老化防止剤、安定剤、シランカップリング剤及び受酸剤などを配合したものである。
(Second Embodiment)
Next, the chloroprene rubber composition according to the second embodiment of the present invention will be described. The chloroprene rubber composition of the present embodiment is obtained by adding a vulcanizing agent, a vulcanization accelerator, a filler, a reinforcing agent, a softening agent, a plasticizer, a lubricant, an anti-aging agent, a stabilizer, and a silane coupling agent to the chloroprene rubber described above. And an acid acceptor.
本実施形態のクロロプレンゴム組成物に添加可能な加硫剤としては、例えば、ベリリウム、マグネシウム、亜鉛、カルシウム、バリウム、ゲルマニウム、チタニウム、錫、ジルコニウム、アンチモン、バナジウム、ビスマス、モリブデン、タングステン、テルル、セレン、鉄、ニッケル、コバルト、オスミウムなどの金属単体、及びこれらの酸化物や水酸化物などを使用することができる。これら金属化合物のなかでも、特に、酸化カルシウムや酸化亜鉛、二酸化アンチモン、三酸化アンチモン、酸化マグネシウムが、加硫効果が高いため好ましい。なお、これらの加硫剤は2種以上を併用して用いてもよい。 Examples of the vulcanizing agent that can be added to the chloroprene rubber composition of the present embodiment include beryllium, magnesium, zinc, calcium, barium, germanium, titanium, tin, zirconium, antimony, vanadium, bismuth, molybdenum, tungsten, tellurium, A simple metal such as selenium, iron, nickel, cobalt, osmium, or an oxide or hydroxide thereof can be used. Among these metal compounds, calcium oxide, zinc oxide, antimony dioxide, antimony trioxide, and magnesium oxide are particularly preferable because of their high vulcanization effect. In addition, you may use these vulcanizing agents in combination of 2 or more types.
また、加硫促進剤としては、例えば、チオウレア系加硫促進剤、チウラム系加硫促進剤、スルフェンアミド系加硫促進剤などを使用することができる。これらの中でも、特に、エチレンチオウレアが、加工性及び加硫物の物性バランスが優れるため、好ましい。なお、これらの加硫剤促進剤は2種以上を併用して用いてもよい。 As the vulcanization accelerator, for example, a thiourea vulcanization accelerator, a thiuram vulcanization accelerator, a sulfenamide vulcanization accelerator, and the like can be used. Among these, ethylenethiourea is particularly preferable because of excellent workability and physical property balance of the vulcanizate. These vulcanizing agent accelerators may be used in combination of two or more.
本実施形態のクロロプレンゴム組成物に配合される充填剤及び補強剤は、通常のクロロプレンゴム用途に使用されているものを用いることができ、例えば、カーボンブラック、シリカ、クレー、タルク、炭酸カルシウムなどが挙げられる。 As the filler and reinforcing agent blended in the chloroprene rubber composition of the present embodiment, those used for ordinary chloroprene rubber applications can be used, for example, carbon black, silica, clay, talc, calcium carbonate, etc. Is mentioned.
また、可塑剤も、通常のクロロプレンゴム用途に使用されている可塑剤を用いることができ、例えば、ジオクチルフタレート、ジオクチルアジペートなどが挙げられる。 Moreover, the plasticizer currently used for the normal chloroprene rubber use can also be used, for example, a dioctyl phthalate, a dioctyl adipate, etc. are mentioned.
老化防止剤としては、通常のクロロプレンゴム用途に使用されている老化防止剤を用いることができる。具体的には、アミン系老化防止剤、イミダゾール系老化防止剤、カルバミン酸金属塩、フェノール系老化防止剤、ワックスなどを使用することができ、これらは単独のみならず併用することもできる。特に、これらの老化防止剤のなかでも、アミン系老化防止剤である4,4’−ビス(α,α−ジメチルベンジル)ジフェニルアミン、オクチル化ジフェニルアミンなどを用いると、成形体の耐熱性を向上させることができる。 As the anti-aging agent, an anti-aging agent used for usual chloroprene rubber applications can be used. Specifically, amine-based antioxidants, imidazole-based antioxidants, carbamic acid metal salts, phenol-based antioxidants, waxes, and the like can be used, and these can be used alone or in combination. In particular, among these anti-aging agents, the use of 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, octylated diphenylamine or the like, which is an amine-based anti-aging agent, improves the heat resistance of the molded article. be able to.
軟化剤としては、通常のクロロプレンゴム用途に使用されている軟化剤を用いることができる。具体的には、潤滑油、プロセスオイル、パラフィン、流動パラフィン、ワセリン、石油アスファルトなどの石油系軟化剤、ナタネ油、アマニ油、ヒマシ油、ヤシ油などの植物油系軟化剤を使用することができ、これらは単独のみならず併用することもできる。 As a softener, the softener currently used for the normal chloroprene rubber use can be used. Specifically, oil-based softeners such as lubricating oil, process oil, paraffin, liquid paraffin, petrolatum, petroleum asphalt, and vegetable oil-based softeners such as rapeseed oil, linseed oil, castor oil, and coconut oil can be used. These can be used not only alone but also in combination.
本実施形態のクロロプレンゴム組成物は、例えばプレス加硫、射出成形加硫、加硫缶加硫、UHF加硫、LCM加硫、HFB加硫などの公知の方法で加硫し、加硫体とすることができる。その際の加硫温度は、クロロプレンゴム組成物の組成や加硫剤の種類によって適宜設定することができるが、通常は140〜190℃の範囲が好ましく、150〜180℃の範囲がより好ましい。 The chloroprene rubber composition of this embodiment is vulcanized by a known method such as press vulcanization, injection molding vulcanization, vulcanization can vulcanization, UHF vulcanization, LCM vulcanization, HFB vulcanization, and the like. It can be. The vulcanization temperature at that time can be appropriately set depending on the composition of the chloroprene rubber composition and the type of the vulcanizing agent, but is usually preferably in the range of 140 to 190 ° C, more preferably in the range of 150 to 180 ° C.
以上詳述したように、本実施形態のクロロプレンゴム組成物は、2,3−ジクロロブタ−1,3−ジエンを特定量含有すると共に、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンを特定量含有する原料モノマーを乳化重合したクロロプレンゴムを使用しているため、効率的にかつ安定して耐結晶性を向上させることができる。その結果、本実施形態のクロロプレンゴム組成物から製造された加硫物では、安定して優れた低温特性が得られる。 As described in detail above, the chloroprene rubber composition of the present embodiment contains a specific amount of 2,3-dichlorobuta-1,3-diene and ap conformation type trans-1-chlorobuta-1,3-. Since the chloroprene rubber obtained by emulsion polymerization of a raw material monomer containing a specific amount of diene and cis-1-chlorobuta-1,3-diene is used, the crystal resistance can be improved efficiently and stably. As a result, the vulcanizate produced from the chloroprene rubber composition of the present embodiment can stably obtain excellent low temperature characteristics.
(第3の実施形態)
次に、本発明の第3の実施形態に係る成形体について説明する。本実施形態の成形体は、前述した第1の実施形態のクロロプレンゴム組成物を、成形後又は成形と同時に加硫して得たものである。成形体の具体例としては、例えば等速ジョイントブーツ、ボールジョイントブーツ、ラック&ピニオンブーツなどのブーツ部品、オイルホース、フューエルベーパーホース、エアホース、ターボチャージャーホース、パワーステアリングホース、ブレーキホース、エアコンホース、高圧ホースなどのホース部品、エンジンマウント防振ゴム、マフラーハンガー、支承ゴム、空気ばね、オイルシールやOリングなどのシール材、及びワイパーブレードなどが挙げられる。
(Third embodiment)
Next, the molded object which concerns on the 3rd Embodiment of this invention is demonstrated. The molded body of this embodiment is obtained by vulcanizing the chloroprene rubber composition of the first embodiment described above after molding or simultaneously with molding. Specific examples of the molded body include boot parts such as constant velocity joint boots, ball joint boots, rack & pinion boots, oil hoses, fuel vapor hoses, air hoses, turbocharger hoses, power steering hoses, brake hoses, air conditioning hoses, Examples include hose parts such as high-pressure hoses, engine mount anti-vibration rubber, muffler hangers, support rubbers, air springs, sealing materials such as oil seals and O-rings, and wiper blades.
その成形方法は、特に限定されるものではないが、プレス成形、射出成形及び押出成形などを適用することができる。例えば、成形体がワイパーブレード又は自動車用防振ゴムや産業用防振ゴムなどの防振材である場合は、プレス成形や射出成形により形成することができる。 The molding method is not particularly limited, and press molding, injection molding, extrusion molding, and the like can be applied. For example, when the molded body is a wiper blade or an anti-vibration material such as an automobile anti-vibration rubber or an industrial anti-vibration rubber, it can be formed by press molding or injection molding.
本実施形態の成形体は、前述した第1の実施形態のクロロプレンゴムを使用しているため、従来に比べて、効率的にかつ安定して、耐結晶性を向上させることができる。その結果、低温下における圧縮永久歪などの低温特性が向上すると共に、この優れた低温特性を安定して得ることができる。 Since the molded body of the present embodiment uses the chloroprene rubber of the first embodiment described above, the crystal resistance can be improved more efficiently and stably than in the past. As a result, the low temperature characteristics such as compression set at low temperatures are improved, and the excellent low temperature characteristics can be stably obtained.
以下、本発明の実施例及び比較例を挙げて、本発明の効果について具体的に説明する。本実施例においては、下記表1に示す組成の原料モノマーを使用して、実施例1〜4及び比較例1〜3のクロロプレンゴムを作製し、その特性について評価した。 Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. In this example, chloroprene rubbers of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared using raw material monomers having the compositions shown in Table 1 below, and their characteristics were evaluated.
次に、これら実施例及び比較例の各クロロプレンゴムを使用し、下記表2に示す配合の組成物を作製し、以下に示す方法及び条件で、「硬さ」、「加工特性」、「引張強度」、「低温圧縮永久歪」について評価した。 Next, using each of the chloroprene rubbers of these Examples and Comparative Examples, a composition having the composition shown in Table 2 below was prepared, and “hardness”, “working characteristics”, “tensile” were used in the following methods and conditions. The strength and the low temperature compression set were evaluated.
(硬さ)
JIS K 6250に基づいてテストピースを作製し(加硫条件:141℃×25分間)、JIS K 6253に基づいて、各加硫物(加硫ゴム)の硬度測定を行った。
(Hardness)
Test pieces were prepared based on JIS K 6250 (vulcanization conditions: 141 ° C. × 25 minutes), and the hardness of each vulcanizate (vulcanized rubber) was measured based on JIS K 6253.
(加工特性)
上記表2に示す組成の各クロロプレンゴム組成物について、JIS K 6300に基づいて、125℃におけるスコーチタイムを測定した。
(Processing characteristics)
For each chloroprene rubber composition having the composition shown in Table 2, the scorch time at 125 ° C. was measured based on JIS K 6300.
(引張強度)
JIS K 6250に基づいてテストピースを作製し(加硫条件:141℃×25分間)、JIS K 6253に基づいて引張試験を行い、各加硫物(加硫ゴム)の強度及び伸びを測定した。
(Tensile strength)
A test piece was prepared based on JIS K 6250 (vulcanization conditions: 141 ° C. × 25 minutes), a tensile test was performed based on JIS K 6253, and the strength and elongation of each vulcanizate (vulcanized rubber) were measured. .
(圧縮永久歪)
上記表2に示す組成の各クロロプレンゴム組成物を、141℃で35分間加硫したものについて、JIS K 6262に基づいて、0℃の温度条件下で70時間試験したときの圧縮永久歪を測定した。
(Compression set)
Measurement of compression set when each chloroprene rubber composition having the composition shown in Table 2 above was vulcanized at 141 ° C. for 35 minutes and tested for 70 hours under a temperature condition of 0 ° C. based on JIS K 6262 did.
また、実施例及び比較例の各クロロプレンゴムを使用して、下記表3に示す配合の組成物を作製し、ゲーマン捻り試験を行った。 Moreover, the composition of the mixing | blending shown in following Table 3 was produced using each chloroprene rubber of an Example and a comparative example, and the Gemann twist test was done.
(ゲーマンT10)
上記表3に示す組成の各ポリクロロプレンゴム組成物を、141℃で25分間加硫したものについて、JIS K 6261に基づいて、ゲーマンねじり試験を実施した。そして、常温における180°ねじりモジュラスの10倍になる温度(T10)を求め、この値により各ポリクロロプレンゴム組成物の低温特性を評価した。
(Geman T10)
A Geman torsion test was carried out based on JIS K 6261 for each of the polychloroprene rubber compositions having the compositions shown in Table 3 above, which was vulcanized at 141 ° C. for 25 minutes. And the temperature (T10) which becomes 10 times the 180 degree torsion modulus in normal temperature was calculated | required, and the low temperature characteristic of each polychloroprene rubber composition was evaluated by this value.
以上の結果を下記表4にまとめて示す。 The above results are summarized in Table 4 below.
上記表4に示すように、2,3−ジクロロブタ−1,3−ジエンは含有するが、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンを含有しない原料モノマーを乳化重合した比較例1のクロロプレンゴムは、低温圧縮永久歪が劣っていた。また、2,3−ジクロロブタ−1,3−ジエン及びap配座型trans−1−クロロブタ−1,3−ジエンを含有しない原料モノマーを乳化重合した比較例2のクロロプレンゴム、並びに、クロロプレンのみを乳化重合した比較例3のクロロプレンゴムも、低温圧縮永久歪が劣っていた。 As shown in Table 4 above, 2,3-dichlorobuta-1,3-diene is contained but ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3 -The chloroprene rubber of Comparative Example 1 obtained by emulsion polymerization of a raw material monomer containing no diene was inferior in low temperature compression set. In addition, the chloroprene rubber of Comparative Example 2 obtained by emulsion polymerization of raw material monomers not containing 2,3-dichlorobuta-1,3-diene and ap conformation type trans-1-chlorobuta-1,3-diene, and chloroprene only The chloroprene rubber of Comparative Example 3 obtained by emulsion polymerization was also inferior in low temperature compression set.
これに対して、ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエン:合計で0.5質量%以上と、2,3−ジクロロブタ−1,3−ジエン:2.0質量%以上とを含有する原料モノマーを乳化重合して得た実施例1〜4のクロロプレンゴムは、低温圧縮永久歪みが良好で、加工性及び機械特性も十分であった。 In contrast, ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene: 0.5% by mass or more in total, 2,3-dichlorobuta- The chloroprene rubbers of Examples 1 to 4 obtained by emulsion polymerization of raw material monomers containing 1,3-diene: 2.0% by mass or more have good low temperature compression set and sufficient workability and mechanical properties. Met.
以上の結果から、本発明によれば、低温特性に優れたクロロプレンゴムが得られることが確認された。 From the above results, according to the present invention, it was confirmed that a chloroprene rubber excellent in low temperature characteristics was obtained.
Claims (2)
ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンのうち少なくとも一方の含有量が異なる複数のクロロプレンを混合することにより、前記原料モノマー中のap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンの総含有量を0.5〜5質量%の範囲に調整するクロロプレンゴムの製造方法。 Chloroprene, ap conformation type trans-1-chlorobuta-1,3-diene, cis-1-chlorobuta-1,3-diene, 2,3-dichlorobuta-1,3-diene: 2.0 to Having a step of emulsion polymerization of a raw material monomer containing at least 20% by mass,
By mixing a plurality of chloroprenes having different contents of at least one of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene, A method for producing chloroprene rubber, wherein the total content of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene is adjusted to a range of 0.5 to 5% by mass .
ap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンのうち少なくとも一方を別途添加することにより、前記原料モノマー中のap配座型trans−1−クロロブタ−1,3−ジエン及びcis−1−クロロブタ−1,3−ジエンの総含有量を0.5〜5質量%の範囲に調整するクロロプレンゴムの製造方法。 Chloroprene, ap conformation type trans-1-chlorobuta-1,3-diene, cis-1-chlorobuta-1,3-diene, 2,3-dichlorobuta-1,3-diene: 2.0 to Having a step of emulsion polymerization of a raw material monomer containing at least 20% by mass,
By adding at least one of ap conformation type trans-1-chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene separately, ap conformation type trans-1 in the raw material monomer is added. -The manufacturing method of the chloroprene rubber which adjusts the total content of chlorobuta-1,3-diene and cis-1-chlorobuta-1,3-diene in the range of 0.5-5 mass% .
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