JP4836134B2 - Novel phosphorus-containing alkadiene polymer and process for producing the same - Google Patents
Novel phosphorus-containing alkadiene polymer and process for producing the same Download PDFInfo
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- JP4836134B2 JP4836134B2 JP2006283110A JP2006283110A JP4836134B2 JP 4836134 B2 JP4836134 B2 JP 4836134B2 JP 2006283110 A JP2006283110 A JP 2006283110A JP 2006283110 A JP2006283110 A JP 2006283110A JP 4836134 B2 JP4836134 B2 JP 4836134B2
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- 229910052698 phosphorus Inorganic materials 0.000 title claims description 37
- 239000011574 phosphorus Substances 0.000 title claims description 35
- 229920000642 polymer Polymers 0.000 title claims description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 33
- 150000001993 dienes Chemical class 0.000 title claims description 21
- 238000000034 method Methods 0.000 title description 2
- -1 alkadiene compounds Chemical class 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 20
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 150000002430 hydrocarbons Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- LOTBYPQQWICYBB-UHFFFAOYSA-N methyl n-hexyl-n-[2-(hexylamino)ethyl]carbamate Chemical compound CCCCCCNCCN(C(=O)OC)CCCCCC LOTBYPQQWICYBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 7
- 239000000178 monomer Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 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 5
- 239000003054 catalyst Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GXXPZLPHLAKYLM-UHFFFAOYSA-N 1-ethylphosphonoylethane Chemical group CCP(=O)CC GXXPZLPHLAKYLM-UHFFFAOYSA-N 0.000 description 1
- UFGGBJYMEZXRLU-UHFFFAOYSA-N 1-methylphosphonoylethane Chemical group CCP(C)=O UFGGBJYMEZXRLU-UHFFFAOYSA-N 0.000 description 1
- DYMNYAUKLJWAIE-UHFFFAOYSA-N 1-methylphosphonoyloxyethane Chemical group CCOP(C)=O DYMNYAUKLJWAIE-UHFFFAOYSA-N 0.000 description 1
- RUNJHCZDNSMWGF-UHFFFAOYSA-N 1-propylphosphonoylpropane Chemical group CCCP(=O)CCC RUNJHCZDNSMWGF-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FPUODXUGDOELAB-UHFFFAOYSA-N CCCOP(=O)CCC Chemical group CCCOP(=O)CCC FPUODXUGDOELAB-UHFFFAOYSA-N 0.000 description 1
- RKXDVGYSGPCUTF-UHFFFAOYSA-N CCOP(=O)CC Chemical group CCOP(=O)CC RKXDVGYSGPCUTF-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- HGDIHUZVQPKSMO-UHFFFAOYSA-N methylphosphonoylmethane Chemical group CP(C)=O HGDIHUZVQPKSMO-UHFFFAOYSA-N 0.000 description 1
- SZZFZADQWWRRTI-UHFFFAOYSA-N methylphosphonoyloxymethane Chemical group COP(C)=O SZZFZADQWWRRTI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical group C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Description
本発明は、難燃剤として有用な、化学構造中にリンを含む新規なアルカジエン重合体とその製造方法に関するものである。 The present invention relates to a novel alkadiene polymer containing phosphorus in its chemical structure, useful as a flame retardant, and a method for producing the same.
化学構造中にリンを含む重合体としては、これまでにオレフィン性不飽和第三級ホスフィンオキシドを単独又は他のエチレン性不飽和化合物と重合させて得られる重合体（特許文献１参照）、ジアミノ置換リン又はそのオキシドで置換された共役ジエン系モノマー又はこれとアニオン共重合可能なモノマーとをアニオン重合触媒の存在下で重合させて得られるリン含有ポリマー（特許文献２参照）、ホスホン酸エステルから誘導される有機基をもつブタジエン化合物の重合体を含むリソグラフィー用反射防止膜形成組成物（特許文献３参照）などが知られている。 Examples of polymers containing phosphorus in the chemical structure include polymers obtained by polymerizing olefinically unsaturated tertiary phosphine oxides alone or with other ethylenically unsaturated compounds (see Patent Document 1), diamino From a phosphonate ester, a phosphorus-containing polymer obtained by polymerizing a conjugated diene monomer substituted with substituted phosphorus or its oxide or a monomer capable of anionic copolymerization thereof in the presence of an anionic polymerization catalyst (see Patent Document 2) An antireflection film-forming composition for lithography containing a polymer of a butadiene compound having an induced organic group (see Patent Document 3) is known.
また、本発明者らは、先に化学構造中にリン原子を含む置換基をもつアルカジエン化合物の製造方法を開発したが（非特許文献１参照）、この重合体は知られていない。 The inventors of the present invention have previously developed a method for producing an alkadiene compound having a substituent containing a phosphorus atom in its chemical structure (see Non-Patent Document 1), but this polymer is not known.
本発明は、難燃剤などとして有用な、新規リン含有アルカジエン重合体及びそれを製造する方法を提供することを目的としてなされたものである。 An object of the present invention is to provide a novel phosphorus-containing alkadiene polymer useful as a flame retardant and the like and a method for producing the same.
本発明者らは、新規なリン含有重合体を開発し、この種の重合体の利用分野を拡大するために、種々研究を重ねた結果、本発明者らが先に開発した、化学構造中にリン原子を含む置換基をもつアルカジエン化合物が、ラジカル開始剤の存在下において容易に重合し、新規な重合体を与えることを見出し、この知見に基づいて本発明をなすに至った。 The present inventors have developed a novel phosphorus-containing polymer and conducted various studies to expand the field of application of this type of polymer. The present inventors have found that an alkadiene compound having a substituent containing a phosphorus atom is easily polymerized in the presence of a radical initiator to give a novel polymer, and based on this finding, the present invention has been made.
すなわち、本発明は、
第一に、一般式（I）
−［ＣＨＲ１−ＣＲ２＝ＣＲ３−ＣＨＲ４］− （I）
［式中のＲ１とＲ２はそれぞれが水素原子又は同一若しくは異なる直鎖状炭化水素基を示すか、或いはＲ１とＲ２が連結して環状炭化水素基を形成する基を示す。
Ｒ３とＲ４はその一方が水素原子を、他方が一般式
−Ｐ（Ｏ）Ｒ５Ｒ６
（ただし、Ｒ５とＲ６はそれぞれ同一若しくは異なるアルキル基、アリール基又はアラルキル基であるか、或いは一方がアルキル基、アリール基又はアラルキル基であり、他方がアルコキシ基、アリールオキシ基又はアラルキルオキシ基である）
で表わされる基を示す］
で表わされる構成単位の少なくとも一種からなるリン含有アルカジエン重合体、及び一般式（II）
ＣＨＲ１＝ＣＲ２−ＣＲ３＝ＣＨＲ４ （II）
（式中のＲ１、Ｒ２、Ｒ３及びＲ４は前記と同じ意味をもつ）
で表わされるアルカジエン化合物の少なくとも１種をラジカル開始剤の存在下で重合させることを特徴とする前記一般式（I）で表わされる構成単位の少なくとも一種からなるリン含有アルカジエン重合体の製造方法を提供するものである。
第二に、 一般式（III）
−［ＣＨＲ１−ＣＲ２＝ＣＲ３−ＣＨＲ４］n−［ＣＨ２―ＣＲ７Ｒ８］ｍ− （III）
［nとｍは、各構成単位の繰り返し数であり、ゼロ以外の任意の数字を表す。式中のＲ１とＲ２はそれぞれが水素原子又は同一若しくは異なる直鎖状炭化水素基を示すか、或いはＲ１とＲ２が連結して環状炭化水素基を形成する基を示す。
Ｒ３とＲ４はその一方が水素原子を、他方が一般式
−Ｐ（Ｏ）Ｒ５Ｒ６
（ただし、Ｒ５とＲ６はそれぞれ同一若しくは異なるアルキル基、アリール基又はアラルキル基であるか、或いは一方がアルキル基、アリール基又はアラルキル基であり、他方がアルコキシ基、アリールオキシ基又はアラルキルオキシ基である）
で表わされる基を示す。Ｒ７は水素原子又は同一若しくは異なる直鎖状炭化水素基を、Ｒ８は水素又は置換されてよい炭化水素基を示す］
で表わされる構成単位の少なくとも一種からなるリン含有アルカジエン重合体、及び
一般式
ＣＨＲ１＝ＣＲ２−ＣＲ３＝ＣＨＲ４ （II）
（式中のＲ１、Ｒ２、Ｒ３及びＲ４は前記と同じ意味をもつ）で表わされるアルカジエン化合物の少なくとも１種を
一般式（IV）
ＣＨ２＝ＣＲ７Ｒ８ （IV）
（Ｒ７は水素原子又は同一若しくは異なる直鎖状炭化水素基を、Ｒ８は水素又は置換されていてもよい炭化水素基を示す）
で表されるアルケン類と、ラジカル開始剤の存在下で、重合させることを特徴とする、前記一般式（III）で表わされる構成単位の少なくとも１種からなるリン含有アルカジエン重合体の製造方法を提供するものである。
That is, the present invention
First, the general formula (I)
- [CHR 1 -CR 2 = CR 3 -CHR 4] - (I)
[R 1 and R 2 in the formula each represent a hydrogen atom or the same or different linear hydrocarbon group, or R 1 and R 2 are linked to form a cyclic hydrocarbon group.
One of R 3 and R 4 is a hydrogen atom, and the other is a general formula —P (O) R 5 R 6
(However, R 5 and R 6 are the same or different alkyl group, aryl group or aralkyl group, respectively, or one is an alkyl group, aryl group or aralkyl group, and the other is an alkoxy group, aryloxy group or aralkyloxy group. Base)
Indicates a group represented by
A phosphorus-containing alkadiene polymer comprising at least one of the structural units represented by formula (II):
CHR 1 = CR 2 -CR 3 = CHR 4 (II)
(Wherein R 1 , R 2 , R 3 and R 4 have the same meaning as above)
And a method for producing a phosphorus-containing alkadiene polymer comprising at least one of the structural units represented by the general formula (I), wherein at least one of the alkadiene compounds represented by the formula is polymerized in the presence of a radical initiator: To do.
Second, the general formula (III)
- [CHR 1 -CR 2 = CR 3 -CHR 4] n- [CH 2 -CR 7 R 8] m - (III)
[N and m are the number of repetitions of each structural unit, and represent any number other than zero. In the formula, R 1 and R 2 each represent a hydrogen atom or the same or different linear hydrocarbon group, or a group in which R 1 and R 2 are linked to form a cyclic hydrocarbon group.
One of R 3 and R 4 is a hydrogen atom, and the other is a general formula —P (O) R 5 R 6
(However, R 5 and R 6 are the same or different alkyl group, aryl group or aralkyl group, respectively, or one is an alkyl group, aryl group or aralkyl group, and the other is an alkoxy group, aryloxy group or aralkyloxy group. Base)
The group represented by is shown. R 7 represents a hydrogen atom or the same or different linear hydrocarbon group, and R 8 represents hydrogen or an optionally substituted hydrocarbon group.
A phosphorus-containing alkadiene polymer comprising at least one of the structural units represented by the general formula: CHR 1 = CR 2 -CR 3 = CHR 4 (II)
(Wherein R 1 , R 2 , R 3 and R 4 have the same meaning as above) at least one of the alkadiene compounds represented by the general formula (IV)
CH 2 = CR 7 R 8 (IV)
(R 7 represents a hydrogen atom or the same or different linear hydrocarbon group, R 8 represents hydrogen or an optionally substituted hydrocarbon group)
A method for producing a phosphorus-containing alkadiene polymer comprising at least one of the structural units represented by the general formula (III), wherein the polymerization is performed in the presence of a alkene represented by the formula: It is to provide.
本発明の前記一般式（I）で示されるリン含有アルカジエン重合体は、具体的には、一般式
で表わされる構成単位、或いはその両方の構成単位からなっている。
また、本発明の前記一般式（III）で示されるリン含有アルカジエン重合体は、具体的には、一般式
で表わされる構成単位、或いはその両方の構成単位からなっている。
The phosphorus-containing alkadiene polymer represented by the general formula (I) of the present invention is specifically represented by the general formula
It consists of a structural unit represented by or both structural units.
Further, the phosphorus-containing alkadiene polymer represented by the general formula (III) of the present invention is specifically represented by the general formula
It consists of a structural unit represented by or both structural units.
上記の式中のＲ１及びＲ２はそれぞれが水素原子又は同一又は異なった直鎖状炭化水素基、好ましくは炭素数１〜４のアルキル基例えばメチル基、エチル基、ｎ‐プロピル基、ｎ‐ブチル基である。また、このＲ１とＲ２とは両者が連結して環状炭化水素基、好ましくは５〜７員環炭化水素基例えばシクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基などを形成する基であってもよい。 R 1 and R 2 in the above formulas are each a hydrogen atom or the same or different linear hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, n -A butyl group. In addition, R 1 and R 2 are linked to form a cyclic hydrocarbon group, preferably a 5- to 7-membered hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like. It may be a group that forms.
また、Ｒ５及びＲ６は、アルキル基好ましくは炭素数１〜４の低級アルキル基、例えばメチル基、エチル基、ｎ‐プロピル基、イソプロピル基、ｎ‐ブチル基、イソブチル基などであるか、アリール基好ましくはフェニル基、トリル基、キシリル基などであるか、又はアラルキル基好ましくはベンジル基、フェネチル基など、及びこれらのアルキル基、アリール基又はアラルキル基をもつアルコキシ基、アリールオキシ基又はアラルキルオキシ基である。 R 5 and R 6 are an alkyl group, preferably a lower alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, An aryl group, preferably a phenyl group, a tolyl group, a xylyl group, or the like, or an aralkyl group, preferably a benzyl group, a phenethyl group, etc., and an alkoxy group, an aryloxy group, or an aralkyl group having an alkyl group, an aryl group, or an aralkyl group. It is an oxy group.
また、Ｒ７は水素原子又は同一若しくは異なる直鎖状炭化水素基を、好ましくは炭素数１〜４のアルキル基例えばメチル基、エチル基、ｎ‐プロピル基、ｎ‐ブチル基である。Ｒ８は水素又は置換されていてもよい炭化水素基を示す。置換されてよい炭化水素基としては、フェニル基、シアノ基、カルボニル置換基、カルボキシル置換基等が挙げられる。
ｎ，ｍは上記構成単位の繰り返し数であり、ゼロ以外の任意に数であるが、好ましくはｎは0.1〜20の数字であり、ｍは80〜99の数字である。
R 7 is a hydrogen atom or the same or different linear hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. R 8 represents hydrogen or an optionally substituted hydrocarbon group. Examples of the hydrocarbon group that may be substituted include a phenyl group, a cyano group, a carbonyl substituent, and a carboxyl substituent.
n and m are the repeating numbers of the above structural units, and are arbitrarily numbers other than zero, preferably n is a number from 0.1 to 20, and m is a number from 80 to 99.
本発明の前記一般式（I）で示されるリン含有アルカジエン重合体は、たとえば、一般式
で表わされるリン含有アルカジエン化合物のいずれか１種或いは両方の混合物をラジカル開始剤の存在下で重合することによって製造することができる。
本発明の前記一般式（III）で示されるリン含有アルカジエン重合体は、前記一般式（II‘）及び一般式（II“）で表わされるリン含有アルカジエン化合物のいずれか１種或いは両方の混合物と、前記一般式（IV）で示されるアルケン類をラジカル開始剤の存在下で重合することによって製造することができる。
The phosphorus-containing alkadiene polymer represented by the general formula (I) of the present invention includes, for example, the general formula
It can manufacture by superposing | polymerizing in the presence of a radical initiator any 1 type of the phosphorus containing alkadiene compound represented by these, or a mixture of both.
The phosphorus-containing alkadiene polymer represented by the general formula (III) of the present invention includes any one or a mixture of the phosphorus-containing alkadiene compounds represented by the general formula (II ′) and the general formula (II “). The alkene represented by the general formula (IV) can be produced by polymerizing in the presence of a radical initiator.
上記の一般式（ＩＩ´）で表わされるリン含有アルカジエン化合物の例としては、１，３‐ブタジエン、１，３‐ペンタジエン、１，３‐ヘキサジエン、２‐（シクロペンテン‐１‐イル）エチレン、２‐（シクロヘキセン‐１‐１‐イル）エチレンなどのジエン化合物の１位に、ジメチルホスフィンオキシド基、ジエチルホスフィンオキシド基、ジプロピルホスフィンオキシド基、メチルエチルホスフィンオキシド基、ジフェニルホスフィンオキシド基、ジトリルホスフィンオキシド基などのジ置換ホスフィンオキシド基が結合した化合物や、メチルホスフィン酸メチルエステル残基、エチルホスフィン酸エチルエステル残基、プロピルホスフィン酸プロピルエステル残基、メチルホスフィン酸エチルエステル残基、フェニルホスフィン酸フェニルエステル残基、トリルホスフィン酸トリルエステル残基などの置換ホスフィン酸エステル残基が結合した化合物を挙げることができる。
また一般式（ＩＩ″）で表わされるリン含有アルカジエン化合物の例としては、上記のジエン化合物の２位に上記のジ置換ホスフィンオキシド基又は置換ホスフィン酸エステル残基が結合した化合物を挙げることができる。
また、一般式（IV）で示されるアルケン類の例として、スチレン、アクリロニトリル、メチルアクリレート、メチールメタアクリレート、アクリル酸、メタアクリル酸などを挙げることができる。
Examples of phosphorus-containing alkadiene compounds represented by the above general formula (II ′) include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2- (cyclopenten-1-yl) ethylene, 2 -(Cyclohexen-1-yl) ethylene and other diene compounds have dimethylphosphine oxide group, diethylphosphine oxide group, dipropylphosphine oxide group, methylethylphosphine oxide group, diphenylphosphine oxide group, ditolylphosphine Compounds with di-substituted phosphine oxide groups such as oxide groups, methylphosphinic acid methyl ester residues, ethylphosphinic acid ethyl ester residues, propylphosphinic acid propyl ester residues, methylphosphinic acid ethyl ester residues, phenylphosphinic acid Eniruesuteru residue, a substituted phosphinic acid ester residue such as tolyl phosphinic acid tolyl ester residue can be exemplified compounds bound.
Examples of the phosphorus-containing alkadiene compound represented by the general formula (II ″) include compounds in which the above disubstituted phosphine oxide group or substituted phosphinic acid ester residue is bonded to the 2-position of the above diene compound. .
Examples of alkenes represented by the general formula (IV) include styrene, acrylonitrile, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid and the like.
上記の一般式（ＩＩ´）又は（ＩＩ″）で表わされるリン含有アルカジエン化合物又はこれらの混合物、またはこれらと一般式（IV）で表されるアルケン類との重合反応は、単に加熱のみによっても進行するが、効率よく重合させるには、ラジカル重合開始剤の存在下で反応させることが必要である。
また、一般式（ＩＩ´）又は（ＩＩ″）で表わされるリン含有アルカジエン化合物又はこれらの混合物、と上記アルケン類との重合反応においては、リン含有アルカジエン化合物とアルケン類との使用割合は、任意でよいが、好ましくは１〜１０００である。
The polymerization reaction of the phosphorus-containing alkadiene compound represented by the above general formula (II ′) or (II ″) or a mixture thereof, or the alkene represented by the general formula (IV) can be performed only by heating. Although it proceeds, it is necessary to carry out the reaction in the presence of a radical polymerization initiator for efficient polymerization.
Further, in the polymerization reaction of the phosphorus-containing alkadiene compound represented by the general formula (II ′) or (II ″) or a mixture thereof and the alkene, the use ratio of the phosphorus-containing alkadiene compound and the alkene is arbitrary. However, it is preferably 1 to 1000.
この際用いるラジカル重合開始剤としては、過酸化物触媒例えば過硫酸カリウム、過硫酸ナトリウム、過酢酸、過酸化ベンゾイル、クメンヒドロペルオキシドやアゾ系触媒例えばアゾビスイソブチロニトリルなどが好ましい。これらの触媒は、単量体のリン含有アルカジエン化合物に基づき０．１〜５０モル％、好ましくは１〜５モル％の範囲で用いられる。 The radical polymerization initiator used in this case is preferably a peroxide catalyst such as potassium persulfate, sodium persulfate, peracetic acid, benzoyl peroxide, cumene hydroperoxide or an azo catalyst such as azobisisobutyronitrile. These catalysts are used in the range of 0.1 to 50 mol%, preferably 1 to 5 mol%, based on the monomeric phosphorus-containing alkadiene compound.
この重合反応は、必ずしも必要ではないが、溶媒中で行うのが有利である。この溶媒としては、ベンゼン、トルエン、キシレンのような芳香族炭化水素系溶媒や、テトラヒドロフラン、テトラヒドロピラン、ジオキサンのような環状エーテル系溶媒が好ましい。 Although this polymerization reaction is not always necessary, it is advantageous to perform it in a solvent. As this solvent, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and cyclic ether solvents such as tetrahydrofuran, tetrahydropyran and dioxane are preferred.
重合温度としては、通常０℃ないし２００℃、好ましくは室温ないし１００℃の範囲が用いられる。この重合反応は、通常大気中で行うが、所望により、不活性雰囲気例えば窒素雰囲気中で行うこともできる。 The polymerization temperature is usually in the range of 0 ° C to 200 ° C, preferably room temperature to 100 ° C. This polymerization reaction is usually performed in the air, but can also be performed in an inert atmosphere such as a nitrogen atmosphere if desired.
このようにして、１〜１００時間反応させることにより、質量平均分子量１０，０００〜１，０００，０００のリン含有アルカジエン重合体を形成させることができる。
重合反応終了後、反応混合物から溶媒を留去し、残留物を水、希酸水溶液で洗浄したのち、真空乾燥することにより、所望の重合体が４０〜９５％の収率で得られる。
In this manner, a phosphorus-containing alkadiene polymer having a mass average molecular weight of 10,000 to 1,000,000 can be formed by reacting for 1 to 100 hours.
After completion of the polymerization reaction, the solvent is distilled off from the reaction mixture, and the residue is washed with water and a dilute aqueous acid solution, followed by vacuum drying, whereby the desired polymer is obtained in a yield of 40 to 95%.
次に実施例により本発明を実施するための最良の形態を説明するが、これにより本発明はなんら限定されるものではない。 Next, the best mode for carrying out the present invention will be described by way of examples. However, the present invention is not limited to these examples.
なお、実施例における質量平均分子量（Ｍｗ）及び難燃性は以下の方法により測定した。
（１）質量平均分子量；
カラムとして、トーソー（Ｔｏｓｏｈ）社製、商品名「ＧＭＨＨＲ−Ｈ＊２」を、また溶媒としてヘキサフルオロイソプロパノールを用い、ポリメチルメタクリレートをスタンダードとしたゲルパーミエーションクロマトグラフィにより測定した。
（２）難燃性；
試料についてＵＬ−９４テストを行い、着火しない場合を難燃性あり、着火した場合を難燃性なしと評価した。
In addition, the mass mean molecular weight (Mw) and flame retardance in an Example were measured with the following method.
(1) mass average molecular weight;
The column was measured by gel permeation chromatography using Tosoh's product name “GMHHR-H * 2” and hexafluoroisopropanol as a solvent and polymethyl methacrylate as a standard.
(2) Flame retardancy;
The sample was subjected to UL-94 test, and the case where it did not ignite was evaluated as flame retardant, and the case where it ignited was evaluated as non-flammable.
実施例１
式
反応終了後、反応混合物から溶媒を留去し、残留物をメタノール１０モルに溶解し、この溶液にヘキサンを加えて生成した重合体を沈殿させることにより、４５％の収率で、モノマー１とモノマー２の重合体を得た。
このものの質量平均分子量（Ｍｗ）は１１０３３、分子量分布（Ｍｗ／Ｍｎ）は１．４であり、難燃性はありと評価された。
また、この重合体の５％質量減は、窒素中で３４４℃、空気中で３４０℃で高い抗酸素酸化性を示した。
Example 1
formula
After completion of the reaction, the solvent was distilled off from the reaction mixture, the residue was dissolved in 10 mol of methanol, and hexane was added to this solution to precipitate the polymer formed, thereby yielding 45% yield of monomer 1 and A polymer of monomer 2 was obtained.
This product had a mass average molecular weight (Mw) of 11033 and a molecular weight distribution (Mw / Mn) of 1.4, and was evaluated as having flame retardancy.
In addition, a 5% mass loss of this polymer showed high antioxidative properties at 344 ° C. in nitrogen and 340 ° C. in air.
実施例２
実施例１で用いたモノマー１の４．１モルとモノマー２の１モルとの混合物をトルエン１０モルに溶解し、触媒としてモノマー１とモノマー２の合計量に基づき２０モル％のＡＩＢＮを添加し、１２０℃において６０時間反応させた。
反応終了後、反応混合物を実施例１と同様に処理することにより５５％の収率でモノマー１とモノマー２の重合体を得た。
このものの質量平均分子量（Ｍｗ）は１９５２４、分子量分布（Ｍｗ／Ｍｎ）は１．４であり、難燃性はありと評価された。
Example 2
A mixture of 4.1 mol of monomer 1 and 1 mol of monomer 2 used in Example 1 was dissolved in 10 mol of toluene, and 20 mol% of AIBN was added as a catalyst based on the total amount of monomer 1 and monomer 2. , And reacted at 120 ° C. for 60 hours.
After completion of the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain a polymer of monomer 1 and monomer 2 in a yield of 55%.
The mass average molecular weight (Mw) of this product was 19524, the molecular weight distribution (Mw / Mn) was 1.4, and it was evaluated that there was flame retardancy.
実施例３−１６
上記と同様な実験操作により、種々の条件下で重合反応を行った。その結果を表１と表２に示した。
Example 3-16
The polymerization reaction was carried out under various conditions by the same experimental procedure as described above. The results are shown in Tables 1 and 2.
実施例１７
メチルメタクリレートとモノマー１と２（1/2=1.45/1）の混合物（メチルメタクリレート/リン化合物＝１００/5）のＴＨＦ溶液（１０Ｍ）にメチルメタクリレート基準で1モル％のＡＩＢＮを加え、70度46時間加熱したところ、共重合高分子が75％の収率で得られた。n/m=1.6/100、Mw=317892,Mw/Mn=1.41.
Example 17
1 mol% of AIBN based on methyl methacrylate is added to a THF solution (10M) of a mixture of methyl methacrylate and monomers 1 and 2 ( 1/2 = 1.45 / 1) (methyl methacrylate / phosphorus compound = 100/5), and 70 degrees When heated for 46 hours, a copolymerized polymer was obtained in a yield of 75%. n / m = 1.6 / 100, Mw = 317892, Mw / Mn = 1.41.
実施例１8−３９
上記と同様な実験操作により、種々のアルケン類との共重合を行った。結果を表３に示した。
Examples 18-39
Copolymerization with various alkenes was carried out by the same experimental procedure as described above. The results are shown in Table 3.
本発明のリン含有アルカジエン重合体は、優れた難燃性を有するので、難燃剤として利用可能である。 Since the phosphorus-containing alkadiene polymer of the present invention has excellent flame retardancy, it can be used as a flame retardant.
Claims (7)
−［ＣＨＲ１−ＣＲ２＝ＣＲ３−ＣＨＲ４］−
［Ｒ１とＲ２はそれぞれが水素原子又は同一若しくは異なる直鎖状炭化水素基を示すか、或いはＲ１とＲ２が連結して環状炭化水素基を形成する基を示す。
Ｒ３とＲ４はその一方が水素原子を、他方が下記一般式
−Ｐ（Ｏ）Ｒ５Ｒ６
（ただし、Ｒ５とＲ６はそれぞれ同一若しくは異なるアルキル基、アリール基又はアラルキル基であるか、或いは一方がアルキル基、アリール基又はアラルキル基であり、他方がアルコキシ基、アリールオキシ基又はアラルキルオキシ基である）
で表わされる基を示す］
で表わされる構成単位の少なくとも一種からなるリン含有アルカジエン重合体。 Formula - [CHR 1 -CR 2 = CR 3 -CHR 4] -
[R 1 and R 2 each represent a hydrogen atom or the same or different linear hydrocarbon group, or a group in which R 1 and R 2 are linked to form a cyclic hydrocarbon group.
One of R 3 and R 4 is a hydrogen atom, and the other is the following general formula —P (O) R 5 R 6
(However, R 5 and R 6 are the same or different alkyl group, aryl group or aralkyl group, respectively, or one is an alkyl group, aryl group or aralkyl group, and the other is an alkoxy group, aryloxy group or aralkyloxy group. Base)
Indicates a group represented by
A phosphorus-containing alkadiene polymer comprising at least one of the structural units represented by:
−［ＣＨＲ１−ＣＲ２＝ＣＲ３−ＣＨＲ４］n−［ＣＨ２―ＣＲ７Ｒ８］ｍ−
［nとｍは、各構成単位の繰り返し数であり、ゼロ以外の任意の数字を表す。Ｒ１とＲ２はそれぞれが水素原子又は同一若しくは異なる直鎖状炭化水素基を示すか、或いはＲ１とＲ２が連結して環状炭化水素基を形成する基を示す。
Ｒ３とＲ４はその一方が水素原子を、他方が一般式
−Ｐ（Ｏ）Ｒ５Ｒ６
（ただし、Ｒ５とＲ６はそれぞれ同一若しくは異なるアルキル基、アリール基又はアラルキル基であるか、或いは一方がアルキル基、アリール基又はアラルキル基であり、他方がアルコキシ基、アリールオキシ基又はアラルキルオキシ基である）
で表わされる基を示す。Ｒ７は水素原子又は同一若しくは異なる直鎖状炭化水素基を、Ｒ８は水素又は置換されていてもよい炭化水素基を示す］
で表わされる構成単位の少なくとも一種からなるリン含有アルカジエン重合体。 Formula - [CHR 1 -CR 2 = CR 3 -CHR 4] n- [CH 2 -CR 7 R 8] m -
[N and m are the number of repetitions of each structural unit, and represent any number other than zero. R 1 and R 2 each represent a hydrogen atom or the same or different linear hydrocarbon group, or a group in which R 1 and R 2 are linked to form a cyclic hydrocarbon group.
One of R 3 and R 4 is a hydrogen atom, and the other is a general formula —P (O) R 5 R 6
(However, R 5 and R 6 are the same or different alkyl group, aryl group or aralkyl group, respectively, or one is an alkyl group, aryl group or aralkyl group, and the other is an alkoxy group, aryloxy group or aralkyloxy group. Base)
The group represented by is shown. R 7 represents a hydrogen atom or the same or different linear hydrocarbon group, and R 8 represents hydrogen or an optionally substituted hydrocarbon group.
A phosphorus-containing alkadiene polymer comprising at least one of the structural units represented by:
−Ｐ（Ｏ）Ｒ５Ｒ６
（ただしＲ５とＲ６はそれぞれ同一若しくは異なるアルキル基、アリール基又はアラルキル基であるか、或いは一方がアルキル基、アリール基又はアラルキル基であり、他方がアルコキシ基、アリールオキシ基又はアラルキルオキシ基である）
で表わされる基を、Ｒ４が水素原子を示す請求項１又は２に記載のリン含有アルカジエン重合体。 R 3 is represented by the general formula —P (O) R 5 R 6.
(However, R 5 and R 6 are the same or different alkyl group, aryl group or aralkyl group, respectively, or one is an alkyl group, aryl group or aralkyl group, and the other is an alkoxy group, aryloxy group or aralkyloxy group. Is)
The phosphorus-containing alkadiene polymer according to claim 1 or 2, wherein R 4 represents a hydrogen atom.
−Ｐ（Ｏ）Ｒ５Ｒ６
（ただしＲ５とＲ６はそれぞれ同一若しくは異なるアルキル基、アリール基又はアラルキル基であるか、或いは一方がアルキル基、アリール基又はアラルキル基であり、他方がアルコキシ基、アリールオキシ基又はアラルキルオキシ基である）
で表わされる基を示す請求項１から３のいずれかに記載のリン含有アルカジエン重合体。 R 3 is a hydrogen atom, R 4 is a general formula —P (O) R 5 R 6
(However, R 5 and R 6 are the same or different alkyl group, aryl group or aralkyl group, respectively, or one is an alkyl group, aryl group or aralkyl group, and the other is an alkoxy group, aryloxy group or aralkyloxy group. Is)
The phosphorus containing alkadiene polymer in any one of Claim 1 to 3 which shows group represented by these.
ＣＨＲ１＝ＣＲ２−ＣＲ３＝ＣＨＲ４
［Ｒ１及びＲ２はそれぞれが水素原子又は同一若しくは異なる直鎖状炭化水素基を示すか或いはＲ１とＲ２とで環状炭化水素基を形成する基を示す。Ｒ３とＲ４はその一方が水素原子を、他方が一般式
−Ｐ（Ｏ）Ｒ５Ｒ６
（Ｒ５とＲ６はそれぞれ同一若しくは異なるアルキル基、アリール基又はアラルキル基であるか、或いは一方がアルキル基、アリール基又はアラルキル基であり、他方がアルコキシ基、アリールオキシ基又はアラルキルオキシ基である）
で表わされる基を示す］
で表わされるアルカジエン化合物の少なくとも１種をラジカル開始剤の存在下で重合させることを特徴とする、一般式
−［ＣＨＲ１−ＣＲ２＝ＣＲ３−ＣＨＲ４］−
（Ｒ１、Ｒ２、Ｒ３及びＲ４は前記と同じ意味をもつ）
で表わされる構成単位の少なくとも一種からなるリン含有アルカジエン重合体の製造方法。 General formula CHR 1 = CR 2 -CR 3 = CHR 4
[R 1 and R 2 each represent a hydrogen atom, the same or different linear hydrocarbon group, or a group that forms a cyclic hydrocarbon group with R 1 and R 2 . One of R 3 and R 4 is a hydrogen atom, and the other is a general formula —P (O) R 5 R 6
(R 5 and R 6 are the same or different alkyl group, aryl group or aralkyl group, respectively, or one is an alkyl group, aryl group or aralkyl group, and the other is an alkoxy group, aryloxy group or aralkyloxy group. is there)
Indicates a group represented by
At least one of the alkadiene compounds represented by the general formula — [CHR 1 —CR 2 ═CR 3 —CHR 4 ] —, which is polymerized in the presence of a radical initiator.
(R 1 , R 2 , R 3 and R 4 have the same meaning as above)
The manufacturing method of the phosphorus containing alkadiene polymer which consists of at least 1 type of the structural unit represented by these.
ＣＨＲ１＝ＣＲ２−ＣＲ３＝ＣＨＲ４
［Ｒ１及びＲ２はそれぞれが水素原子又は同一若しくは異なる直鎖状炭化水素基を示すか或いはＲ１とＲ２とで環状炭化水素基を形成する基を示す。
Ｒ３とＲ４はその一方が水素原子を、他方が一般式
−Ｐ（Ｏ）Ｒ５Ｒ６
（Ｒ５とＲ６はそれぞれ同一若しくは異なるアルキル基、アリール基又はアラルキル基であるか、或いは一方がアルキル基、アリール基又はアラルキル基であり、他方がアルコキシ基、アリールオキシ基又はアラルキルオキシ基である）
で表わされる基を示す］
で表わされるアルカジエン化合物の少なくとも１種を、一般式
ＣＨ２＝ＣＲ７Ｒ８
（Ｒ７は水素原子又は同一若しくは異なる直鎖状炭化水素基を、Ｒ８は水素又は置換されていてもよい炭化水素基を示す）
で表されるアルケン類と、ラジカル開始剤の存在下で、重合させることを特徴とする、一般式
−［ＣＨＲ１−ＣＲ２＝ＣＲ３−ＣＨＲ４］n−［ＣＨ２―ＣＲ７Ｒ８］ｍ−
（ｎ、ｍ、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ７及びＲ８は同じ意味をもつ）
で表わされる構成単位の少なくとも一種からなるリン含有アルカジエン重合体の製造方法。 General formula CHR 1 = CR 2 -CR 3 = CHR 4
[R 1 and R 2 each represent a hydrogen atom, the same or different linear hydrocarbon group, or a group that forms a cyclic hydrocarbon group with R 1 and R 2 .
One of R 3 and R 4 is a hydrogen atom, and the other is a general formula —P (O) R 5 R 6
(R 5 and R 6 are the same or different alkyl group, aryl group or aralkyl group, respectively, or one is an alkyl group, aryl group or aralkyl group, and the other is an alkoxy group, aryloxy group or aralkyloxy group. is there)
Indicates a group represented by
At least one alkadiene compound represented by the general formula CH 2 ═CR 7 R 8
(R 7 represents a hydrogen atom or the same or different linear hydrocarbon group, R 8 represents hydrogen or an optionally substituted hydrocarbon group)
And alkenes represented in the presence of a radical initiator, characterized by polymerizing the general formula - [CHR 1 -CR 2 = CR 3 -CHR 4] n- [CH 2 -CR 7 R 8 ] M −
(N, m, R 1 , R 2 , R 3 , R 4 , R 7 and R 8 have the same meaning)
The manufacturing method of the phosphorus containing alkadiene polymer which consists of at least 1 type of the structural unit represented by these.
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