JPH03413B2 - - Google Patents
Info
- Publication number
- JPH03413B2 JPH03413B2 JP11233482A JP11233482A JPH03413B2 JP H03413 B2 JPH03413 B2 JP H03413B2 JP 11233482 A JP11233482 A JP 11233482A JP 11233482 A JP11233482 A JP 11233482A JP H03413 B2 JPH03413 B2 JP H03413B2
- Authority
- JP
- Japan
- Prior art keywords
- bis
- oxazoline
- acid
- oxazolinyl
- phosphite
- 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.)
- Expired
Links
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 8
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- -1 phosphorous acid ester Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VMNKHSPZIGIPLL-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OCC(CO)(CO)COP(O)O VMNKHSPZIGIPLL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical class CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- IFIUFEBEPGGBIJ-UHFFFAOYSA-N 4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC=N1 IFIUFEBEPGGBIJ-UHFFFAOYSA-N 0.000 description 1
- CIIILUMBZOGKDF-UHFFFAOYSA-N 5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=CO1 CIIILUMBZOGKDF-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QYFJGARGTVLRDI-UHFFFAOYSA-N OP(O)OP(O)O.CC(COC(C)CO)O Chemical compound OP(O)OP(O)O.CC(COC(C)CO)O QYFJGARGTVLRDI-UHFFFAOYSA-N 0.000 description 1
- LZNWGSIDNAGRAJ-UHFFFAOYSA-N P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 Chemical compound P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 LZNWGSIDNAGRAJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000003156 secondary amide group Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- XGVXKJKTISMIOW-ZDUSSCGKSA-N simurosertib Chemical compound N1N=CC(C=2SC=3C(=O)NC(=NC=3C=2)[C@H]2N3CCC(CC3)C2)=C1C XGVXKJKTISMIOW-ZDUSSCGKSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003142 tertiary amide group Chemical group 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyamides (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】 本発明は熱硬化性樹脂の製造法に関する。[Detailed description of the invention] The present invention relates to a method for producing thermosetting resins.
ビス（２−オキサゾリン）化合物とジカルボン
酸をほゞ等モル混合し、加熱すると線状のポリエ
ステルアミドが生成することはよく知られたこと
である。 It is well known that when a bis(2-oxazoline) compound and a dicarboxylic acid are mixed in approximately equimolar amounts and heated, a linear polyesteramide is produced.
本発明者らは上記反応について詳細に検討した
ところ、下記のように一旦、生成したアミド結合
にオキサゾリン環が一部開環付加する副反応がお
き、このため十分大きな分子量の線状ポリエステ
ルアミドが生成しにくいことを知見した。 The present inventors investigated the above reaction in detail, and found that a side reaction occurs in which the oxazoline ring is partially ring-opened and added to the generated amide bond, as shown below, and as a result, a linear polyester amide with a sufficiently large molecular weight We found that it is difficult to generate.
このアミド基とオキサゾリン環との反応を利用
すればビス（２−オキサゾリン）化合物とジカル
ボン酸とから熱硬化性樹脂が得られるはずである
が、アミド基とオキサゾリン環との反応速度が極
めて遅く、実用的な条件では熱硬化性樹脂を得る
ことは困難である。 If this reaction between the amide group and the oxazoline ring is used, a thermosetting resin should be obtained from the bis(2-oxazoline) compound and the dicarboxylic acid, but the reaction rate between the amide group and the oxazoline ring is extremely slow. It is difficult to obtain thermosetting resins under practical conditions.
本発明者らはアミド基とオキサゾリン環との反
応を選択的に促進する触媒について鋭意検討した
ところ、有機リン化合物のなかで亜リン酸エステ
ルが有効であることを知見し、これらの知見にも
とづいて本発明を完成するに至つた。 The present inventors conducted intensive studies on catalysts that selectively promote the reaction between amide groups and oxazoline rings, and found that phosphorous esters are effective among organic phosphorus compounds.Based on these findings, As a result, the present invention was completed.
すなわち、本発明は、ビス（２−オキサゾリ
ン）化合物とジカルボン酸とをビス（２−オキサ
ゾリン）化合物１モルに対してジカルボン酸を約
１モル以下の割合で亜リン酸エステルの存在下、
加熱反応させることを特徴とする熱硬化性樹脂の
製造法である。 That is, the present invention comprises a bis(2-oxazoline) compound and a dicarboxylic acid in the presence of a phosphorous acid ester in a ratio of about 1 mole or less of dicarboxylic acid per 1 mole of the bis(2-oxazoline) compound,
This is a method for producing a thermosetting resin characterized by carrying out a heating reaction.
本発明に用いられるビス（２−オキサゾリン）
化合物としては、たとえば１，２−ビス（２−オ
キサゾリニル−２）エタン、１，４−ビス（２−
オキサゾリニル−２）ブタン、１，６−ビス（２
−オキサゾリニル−２）ヘキサン、１，８−ビス
（２−オキサゾリニル−２）オクタン、１，４−
ビス（２−オキサゾリニル−２）シクロヘキサン
などのアルキル鎖にオキサゾリン環が結合した化
合物、たとえば１，２−ビス（２−オキサゾリニ
ル−２）ベンゼン、１，３−ビス（２−オキサゾ
リニル−２）ベンゼン、１，４−ビス（２−オキ
サゾリニル−２）ベンゼン，５，5′−ジメチル−
２，2′−ビス（２−オキサゾリニル−２）ベンゼ
ン、４，４，4′，4′−テトラメチル−２，2′−ビ
ス（２−オキサゾリニル−２）ベンゼン、１，２
−ビス（５−メチル−２−オキサゾリニル−２）
ベンゼン、１，３−ビス（５−メチル−２−オキ
サゾリニル−２）ベンゼン、１，４−ビス（５−
メチル−２−オキサゾリニル−２）ベンゼンなど
の芳香核に２個のオキサゾリン環が結合したもの
で、下記一般式で表わされるものおよび２，2′−
ビス（オキサゾリン）、２，2′−ビス（４−メチ
ル−２−オキサゾリン）、２，2′−ビス（５−メ
チル−２−オキサゾリン）などがあげられる。 Bis(2-oxazoline) used in the present invention
Examples of the compound include 1,2-bis(2-oxazolinyl-2)ethane, 1,4-bis(2-
Oxazolinyl-2)butane, 1,6-bis(2)
-oxazolinyl-2)hexane, 1,8-bis(2-oxazolinyl-2)octane, 1,4-
Compounds in which an oxazoline ring is bonded to an alkyl chain such as bis(2-oxazolinyl-2)cyclohexane, such as 1,2-bis(2-oxazolinyl-2)benzene, 1,3-bis(2-oxazolinyl-2)benzene, 1,4-bis(2-oxazolinyl-2)benzene, 5,5'-dimethyl-
2,2'-bis(2-oxazolinyl-2)benzene, 4,4,4',4'-tetramethyl-2,2'-bis(2-oxazolinyl-2)benzene, 1,2
-bis(5-methyl-2-oxazolinyl-2)
Benzene, 1,3-bis(5-methyl-2-oxazolinyl-2)benzene, 1,4-bis(5-
Methyl-2-oxazolinyl-2) Two oxazoline rings are bonded to an aromatic nucleus such as benzene, and those represented by the following general formula and 2,2'-
Examples include bis(oxazoline), 2,2'-bis(4-methyl-2-oxazoline), and 2,2'-bis(5-methyl-2-oxazoline).
〔式中、R′は２価の炭化水素基を、R1〜R4は
水素または炭化水素基を示す。〕
ジカルボン酸としては、たとえばマロン酸、コ
ハク酸、アジピン酸、ピメリン酸、スベリン酸、
アゼライン酸、セバシン酸、ドデカン二酸、ダイ
マー酸、エイコサン二酸などの脂肪族ジカルボン
酸、たとえばフタル酸、イソフタル酸、ナフタレ
ンジカルボン酸、ジフエニルスルホンジカルボン
酸、ジフエニルメタンジカルボン酸などの芳香族
ジカルボン酸でビス（２−オキサゾリン）化合物
との混合加熱時に溶融するものが使用可能であ
る。これらは二種以上混合して用いてもよい。 [In the formula, R' represents a divalent hydrocarbon group, and R 1 to R 4 represent hydrogen or a hydrocarbon group. ] Examples of dicarboxylic acids include malonic acid, succinic acid, adipic acid, pimelic acid, suberic acid,
Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosanedioic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenylmethane dicarboxylic acid. An acid that melts when mixed and heated with a bis(2-oxazoline) compound can be used. Two or more of these may be used in combination.
ジカルボン酸の量はビス（２−オキサゾリン）
化合物１モルに対して約１モル以下、好ましくは
約１〜0.2モル程度である。触媒として用いられ
る亜リン酸エステルとしては、たとえば亜リン酸
トリフエニル、亜リン酸トリス（ノニルフエニ
ル）、亜リン酸トリエチル、亜リン酸トリ−ｎ−
ブチル、亜リン酸トリス（２−エチルヘキシル）、
亜リン酸トリステアリル、亜リン酸ジフエニルモ
ノデシル、テトラフエニル、ジプロピレングリコ
ールジホスフアイト、テトラフエニルテトラ（ト
リデシル）ペンタエリスリトールテトラホスフア
イト、亜リン酸ジフエニル、亜リン酸４，4′−ブ
チリデンビス（３−メチル−６−ｔ−ブチルフエ
ニル−ジ−ドリデシル）、ビスフエノールＡ ペ
ンタエリスリトールホスフアイトなどのジエステ
ル、トリエステルがあげられる。これらは二種以
上用いてもよい。 The amount of dicarboxylic acid is bis(2-oxazoline)
The amount is about 1 mol or less, preferably about 1 to 0.2 mol, per 1 mol of the compound. Examples of phosphite esters used as catalysts include triphenyl phosphite, tris(nonylphenyl) phosphite, triethyl phosphite, and tri-n-phosphite.
Butyl, tris(2-ethylhexyl) phosphite,
Tristearyl phosphite, diphenyl monodecyl phosphite, tetraphenyl, dipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, diphenyl phosphite, 4,4'-butylidenebis phosphite (3-methyl-6-t-butylphenyl-didoridecyl), bisphenol A pentaerythritol phosphite, and other diesters and triesters. Two or more types of these may be used.
上記のなかでフエノレート基あるいは置換フエ
ノレート基を含む亜リン酸エステルが特に好まし
い。 Among the above, phosphorous acid esters containing a phenolate group or a substituted phenolate group are particularly preferred.
触媒の量はビス（２−オキサゾリン）化合物と
ジカルボン酸との和に対して約0.05重量％以上、
好ましくは約0.2重量％以上である。 The amount of the catalyst is about 0.05% by weight or more based on the sum of the bis(2-oxazoline) compound and dicarboxylic acid,
Preferably it is about 0.2% by weight or more.
ビス（２−オキサゾリン）化合物とジカルボン
酸とは、最初から混合しておいてもよいが、それ
ぞれを加温しておき、高温で混合することも可能
である。触媒の添加に関しては、最初から混合し
ておく、加温の途中で混合する、ビス（２−オキ
サゾリン）化合物またはジカルボン酸のいずれか
に混合しておくの三通りがあげられるが、どの手
段をとつてもよい。 The bis(2-oxazoline) compound and dicarboxylic acid may be mixed from the beginning, but it is also possible to heat each of them and mix them at a high temperature. There are three ways to add the catalyst: mixing it from the beginning, mixing it during heating, and mixing it with either the bis(2-oxazoline) compound or the dicarboxylic acid. Very good.
反応温度は約100℃以上、好ましくは約150゜〜
250℃程度である。 The reaction temperature is approximately 100°C or higher, preferably approximately 150°C or higher.
The temperature is around 250℃.
反応時間は触媒の種類や量、ビス（２−オキサ
ゾリン）化合物やジカルボン酸の種類などによつ
て一概には言えないが、通常、約２分〜１時間程
度である。 Although the reaction time cannot be determined unconditionally depending on the type and amount of the catalyst, the type of bis(2-oxazoline) compound and dicarboxylic acid, etc., it is usually about 2 minutes to 1 hour.
本発明により得られる熱硬化性樹脂は分子内に
エステル基、第２アミド基および第３アミド基を
有し、強靭で、耐摩もう性、耐溶媒性にすぐれて
いる。そして原料の種類、ビス（２−オキサゾリ
ン）化合物とジカルボン酸とのモル比、触媒の種
類と量を適宜変えることによつて、かなり広範囲
の物性を有した熱硬化性樹脂を得ることができ
る。この熱硬化性樹脂はたとえばロール、歯車な
どの機械部品の成型、電気部品のうめ込み成型、
電気絶縁物、歯科材料などに用いることができ
る。 The thermosetting resin obtained by the present invention has an ester group, a secondary amide group, and a tertiary amide group in the molecule, and is strong and has excellent abrasion resistance and solvent resistance. By appropriately changing the type of raw materials, the molar ratio of the bis(2-oxazoline) compound and dicarboxylic acid, and the type and amount of the catalyst, thermosetting resins having a fairly wide range of physical properties can be obtained. This thermosetting resin can be used, for example, to mold mechanical parts such as rolls and gears, and to embed electrical parts.
It can be used for electrical insulators, dental materials, etc.
以下に実施例ならびに比較例をあげ、本発明を
更に具体的に説明する。 EXAMPLES The present invention will be explained in more detail by giving Examples and Comparative Examples below.
実施例 １
１，３−ビス（２−オキサゾリニル−２）ベン
ゼン108ｇ（0.5モル）、アジピン酸73ｇ（0.5モ
ル）、亜リン酸トリフエニル1.8ｇを乳鉢でよく混
合し、200℃の金型に入れた。内温が180℃を越え
てから20分間金型の温度を200℃に保ち、それ以
後放冷して140℃以下になつてからとり出すと、
透明な硬化物が得られた。この硬化物は200℃以
上でも形態を保つており、270℃以上で徐々に分
解する。Example 1 108 g (0.5 mol) of 1,3-bis(2-oxazolinyl-2)benzene, 73 g (0.5 mol) of adipic acid, and 1.8 g of triphenyl phosphite were mixed well in a mortar and placed in a mold at 200°C. Ta. After the internal temperature exceeds 180℃, keep the mold temperature at 200℃ for 20 minutes, then let it cool down to below 140℃ before taking it out.
A transparent cured product was obtained. This cured product maintains its shape even above 200°C and gradually decomposes above 270°C.
比較例
１，３−ビス（２−オキサゾリニル−２）ベン
ゼン108ｇとアジピン酸73ｇとを乳鉢でよく混合
し200℃の金型に入れた。内温が180℃を越えてか
ら20分間金型の温度を200℃に保ち、それ以後放
冷して常温附近まで温度が下がつてからとり出す
と透明な硬化物が得られた。この硬化物は50〜60
℃で軟化し、100℃以上で押さえると形がくずれ
てしまう。Comparative Example 108 g of 1,3-bis(2-oxazolinyl-2)benzene and 73 g of adipic acid were thoroughly mixed in a mortar and placed in a mold at 200°C. After the internal temperature exceeded 180°C, the temperature of the mold was kept at 200°C for 20 minutes, and then allowed to cool, allowing the temperature to drop to around room temperature before being removed, yielding a transparent cured product. This cured product is 50 to 60
It softens at temperatures above 100°C and loses its shape if pressed at temperatures above 100°C.
実施例 ２
１，３−ビス（２−オキサゾリニル−２）ベン
ゼン154ｇ（0.75モル）、アジピン酸36.5ｇ（0.25
モル）、亜リン酸トリフエニル0.95ｇを乳鉢でよ
く混合し、170℃の金属性反応容器に入れた。１
分30秒後には溶融して液状となり、13分後にゲル
化し、14分後に硬化した。その後20分間そのまゝ
加温してから冷却して、非常に固い硬化物を得
た。このものの23℃におけるシヨア硬度Ｄは95で
あり、160℃においても90であつた。Example 2 154 g (0.75 mol) of 1,3-bis(2-oxazolinyl-2)benzene, 36.5 g (0.25 mol) of adipic acid
mol) and 0.95 g of triphenyl phosphite were thoroughly mixed in a mortar and placed in a metal reaction vessel at 170°C. 1
It melted and became liquid after 30 minutes, turned into a gel after 13 minutes, and hardened after 14 minutes. Thereafter, it was heated for 20 minutes and then cooled to obtain a very hard cured product. The Shore hardness D of this product was 95 at 23°C and 90 at 160°C.
実施例 ３
１，３−ビス（２−オキサゾリニル−２）ベン
ゼン43.3ｇ（0.2モル）、セバシン酸20.2ｇ（0.1モ
ル）、亜リン酸ジフエニルモノデシル0.6ｇを乳鉢
でよく混合し、170℃の金属性反応容器に入れた。
２分後には溶融して液状になり、14分後にゲル化
した。その後10分間はそのまゝの温度を保ち、そ
れから190℃に温度を上げて10分間保つた後、放
冷して硬化物を得た。この硬化物は融点を持た
ず、分解温度は約280℃であつた。Example 3 43.3 g (0.2 mol) of 1,3-bis(2-oxazolinyl-2)benzene, 20.2 g (0.1 mol) of sebacic acid, and 0.6 g of diphenylmonodecyl phosphite were mixed well in a mortar and heated to 170°C. into a metal reaction vessel.
It melted and became liquid after 2 minutes, and gelled after 14 minutes. After that, the temperature was kept as it was for 10 minutes, then the temperature was raised to 190°C, kept for 10 minutes, and then allowed to cool to obtain a cured product. This cured product had no melting point and had a decomposition temperature of about 280°C.
実施例 ４
１，４−ビス（２−オキサゾリニル−２）ベン
ゼン42.2ｇ（0.195モル）、ドデカン二酸29.9ｇ
（0.13モル）、ビスフエノールＡペンタエリスリト
ールフオスフアイト0.72ｇを乳鉢でよく混合し、
200℃の金属性反応容器に入れた。内温が180℃を
越えてから７分後にゲル化した。そのまゝ20分間
保つた後、放冷して淡黄色ほゞ透明の不溶不融の
硬化物を得た。Example 4 1,4-bis(2-oxazolinyl-2)benzene 42.2g (0.195mol), dodecanedioic acid 29.9g
(0.13 mol) and 0.72 g of bisphenol A pentaerythritol phosphite were mixed well in a mortar.
It was placed in a metal reaction vessel at 200°C. Gelation occurred 7 minutes after the internal temperature exceeded 180°C. After keeping it as it was for 20 minutes, it was allowed to cool to obtain a pale yellow, almost transparent, insoluble and infusible cured product.
実施例 ５
１，３−ビス（２−オキサゾリニル−２）ベン
ゼン42.2ｇ（0.195モル）、イソフタール酸21.6ｇ
（0.13モル）、亜リン酸トリフエニル0.64ｇを乳鉢
でよく混合し、200℃の金属性反応容器に入れた。
150℃を越えると全体が流動性をおび、195℃でゲ
ル化した。そのまゝ15分間加熱した後、冷却し
て、不溶不融の非常に固い硬化物を得た。Example 5 1,3-bis(2-oxazolinyl-2)benzene 42.2g (0.195mol), isophthalic acid 21.6g
(0.13 mol) and 0.64 g of triphenyl phosphite were thoroughly mixed in a mortar and placed in a metal reaction vessel at 200°C.
When the temperature exceeded 150°C, the entire mixture became fluid, and at 195°C it became a gel. After heating for 15 minutes, the mixture was cooled to obtain an insoluble and extremely hard cured product.
Claims (1)
ン酸とをビス（２−オキサゾリン）化合物１モル
に対してジカルボン酸を約１モル以下の割合で亜
リン酸エステルの存在下、加熱反応させることを
特徴とする熱硬化性樹脂の製造法。1 A bis(2-oxazoline) compound and a dicarboxylic acid are heated to react in the presence of a phosphite at a ratio of about 1 mole or less of dicarboxylic acid to 1 mole of the bis(2-oxazoline) compound. A method for producing thermosetting resin.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11233482A JPS591533A (en) | 1982-06-28 | 1982-06-28 | Production of thermosetting resin |
| US06/504,781 US4474942A (en) | 1982-06-28 | 1983-06-16 | Cross-linked polyesteramide from bis(2-oxazoline) |
| DE8383106215T DE3361216D1 (en) | 1982-06-28 | 1983-06-25 | Cross-linked polyesteramides and production thereof |
| EP83106215A EP0097937B1 (en) | 1982-06-28 | 1983-06-25 | Cross-linked polyesteramides and production thereof |
| CA000431244A CA1192346A (en) | 1982-06-28 | 1983-06-27 | Cross-linked polyesteramides and production thereof |
| KR1019830002913A KR920002620B1 (en) | 1982-06-28 | 1983-06-28 | Process for the preparation of thermosetting resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11233482A JPS591533A (en) | 1982-06-28 | 1982-06-28 | Production of thermosetting resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS591533A JPS591533A (en) | 1984-01-06 |
| JPH03413B2 true JPH03413B2 (en) | 1991-01-08 |
Family
ID=14584076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11233482A Granted JPS591533A (en) | 1982-06-28 | 1982-06-28 | Production of thermosetting resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS591533A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5968330A (en) * | 1982-10-12 | 1984-04-18 | Takeda Chem Ind Ltd | Production of crosslinked amide polymer |
| JPH02145230A (en) * | 1988-11-24 | 1990-06-04 | Mitsubishi Automob Eng Co Ltd | Automatic fitting device for bearing cap |
| JPH0236231A (en) * | 1989-03-31 | 1990-02-06 | Takeda Chem Ind Ltd | Production of resin |
| US5236112A (en) * | 1991-07-31 | 1993-08-17 | Mont-Bell Co., Ltd. | Back bag |
| JP4982989B2 (en) * | 2005-09-27 | 2012-07-25 | 住友ベークライト株式会社 | Reaction product of polyvalent carboxylic acid and bisoxazoline, and production method thereof |
-
1982
- 1982-06-28 JP JP11233482A patent/JPS591533A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS591533A (en) | 1984-01-06 |
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