JPH0411574B2 - - Google Patents
Info
- Publication number
- JPH0411574B2 JPH0411574B2 JP63111821A JP11182188A JPH0411574B2 JP H0411574 B2 JPH0411574 B2 JP H0411574B2 JP 63111821 A JP63111821 A JP 63111821A JP 11182188 A JP11182188 A JP 11182188A JP H0411574 B2 JPH0411574 B2 JP H0411574B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- polymer
- esterification reaction
- esterification
- compound
- 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 - Lifetime
Links
- 238000005886 esterification reaction Methods 0.000 claims description 43
- -1 polybutylene terephthalate Polymers 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 238000006068 polycondensation reaction Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 19
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 18
- 150000003609 titanium compounds Chemical class 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 33
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 230000009849 deactivation Effects 0.000 description 12
- 230000032050 esterification Effects 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- ZUHPIMDQNAGSOV-UHFFFAOYSA-N 2-benzyl-2-phenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)(C(O)=O)CC1=CC=CC=C1 ZUHPIMDQNAGSOV-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000252505 Characidae Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
［産業上の利用分野］
本発明は高重合度ポリブチレンテレフタレート
（以下、PBTという）の製造方法、さらに詳しく
はテレフタル酸（以下、TPAという）と、１，
４−ブタンジオール（以下、BGという）とを主
な出発原料とする直接重合法（以下直重法とい
う）において、そのエステル化反応に特定の添加
剤を適用することによつて高重合度PBTを短時
間で製造する方法に関するものである。
［従来技術］
今日、PBTは成形性、耐熱性、耐薬品性など
卓越した特性を活かして電気用部品、自動者用部
品などの成形用樹脂として、またソフト性、スト
レツチ性を活かして繊維用としても、その用途が
拡大しつつある。
さて、PBTの製造において、直重法はその反
応過程において副生物の全て回収、再利用するこ
とが可能なため経済的であり、また省資源的にも
も優れたプロセスと一般に認められている。
かかるPBTの直重法、特にエステル化反応に
は、触媒の存在が不可欠であり、その触媒として
有機チタン化合物が広く用いられている。
しかし、有機チタン化合物（例えばチタン酸エ
ステル）は、エステル化反応触媒として優れた触
媒活性を示す一方、その反応やBGの分解（脱水
環化）で副生する水によつて加水分解を受け、不
溶性異物の生成や、触媒としての活性低下を起こ
し易い。このようなエステル化段階での不溶性異
物の生成や触媒活性の低下問題は、当然はがら反
応時間の短縮化にとつて阻害因子となるばかり
か、反応生成物の透明性を著しく低下させ、ひい
ては重合反応性の低下のため所望の重合度が得ら
れず、場合によつては重縮合反応の“頭打ち”現
象を起したり、更にポリマの成形過程では不溶性
異物に由来する成形性の低下や成型品の品質低下
などの問題が惹起するようになる。
かかる有機チタン化合物の不溶化・失活問題に
対して、有機チタン化合物をエステル化反応率50
％を境に前半、後半各々に添加する、添加方法の
改善（例えば特開昭49−57092号公報）などが提
案されているが、有機チタン化合物の不溶化・失
活問題はあまり改善されず、効果に限界がある。
また、多価アルコール系化合物とアルカリ金属
化合物とを併用するなどの手段（例えば特開昭62
−225524公報）、アルカノールアミンチタン酸エ
ステル化合物を触媒として用いる手段（例えば特
開昭62−141022公報）、有機チタン化合物とアル
カノールアミン化合物とを併用するなどの手段
（例えば特開昭62−199617公報）が提案されてい
るが、これらの手段によつてポリマの重合反応性
がある程度改良されるとは言え、エステル化段階
における有機チタン化合物の不溶化・失活問題は
依然未解決であるばかりか、この不溶化・失活に
基づくポリマ色調の低下や、増粘性が大きいなど
の問題があつた。従つて、直重法により高重合度
のPBTを短時間で製造するためには、エステル
化段階における有機チタン化合物触媒の加水分解
による不溶化・失活問題を如何にして解決するか
が当技術分野での重要な検討課題であつた。
［発明が解決しようとする課題］
本発明の課題は、直重法によるPBTの製造、
特にそのエステル化反応における有機チタン触媒
の不溶化・失活を抑制し、反応時間の短縮を図る
ことにある。また他の課題はエステル化反応にお
ける有機チタン触媒の不溶化・失活を抑制するこ
とによつて不溶性異物の生成、分岐構造の生成に
よる増粘現象、ポリマの着色、成形品物性や繊維
物性の低下などの諸問題を解消することにある。
［課題を解決するための手段］
本発明の上記課題は、テレフタル酸を主とする
ジカルボン酸成分とブタンジオールを主とするグ
リコール成分とから、エステル化反応及び重縮合
反応を経由してポリブチレンテレフタレートを製
造するに際し、前記エステル化反応をヒンダード
フエノール系化合物および有機チタン化合物の存
在下で行なうことによつて、解決することができ
る。
以下、本発明の構成を具体的に説明するが、先
ず本発明の骨子であるPBTのエステル化反応に
用いるヒンダードフエノール系化合物と有機チタ
ン触媒について述べる。
すなわち、本発明においては、エステル化反応
に際し、必ずヒンダードフエノール系化合物、即
ち、OH基の隣接位に立体障害となる置換基を有
するフエノール化合物を存在させておく必要があ
る。
従来、この種のヒンダードフエノール系化合物
をPBTの溶融重縮合もしくは固相重合段階で用
いることは公知である（例えば、特公昭55−7853
号公報、特公昭58−34493号公報など）。しかし、
これらの技術は溶融重縮合ないし固相重合時にお
けるポリマーの酸化分解の防止を課題とするもの
で、ヒンダードフエノール系化合物がエステル化
段階における有機チタン触媒の不溶化・失活に対
して極めて効果的に作用すること等については全
く示されていない。
この種のヒンダードフエノール系化合物の例と
しては、下記式［］〜［］で表されるヒンダ
ードフエノール系化合物である。
ただし、Ｘは１〜４の整数であり、R1は炭素
数１〜20のアルキル基、R2は
[Industrial Application Field] The present invention relates to a method for producing highly polymerized polybutylene terephthalate (hereinafter referred to as PBT), more specifically, a method for producing terephthalic acid (hereinafter referred to as TPA), 1.
In the direct polymerization method (hereinafter referred to as direct polymerization method) using 4-butanediol (hereinafter referred to as BG) as the main starting material, high polymerization degree PBT is produced by applying specific additives to the esterification reaction. The present invention relates to a method for manufacturing in a short time. [Conventional technology] Today, PBT is used as a molding resin for electrical parts and automobile parts by taking advantage of its excellent properties such as moldability, heat resistance, and chemical resistance, and it is also used for textiles by taking advantage of its softness and stretchability. However, its uses are expanding. Now, in the production of PBT, the direct weight method is economical as it is possible to recover and reuse all by-products during the reaction process, and is generally recognized as an excellent process in terms of resource conservation. . The presence of a catalyst is essential for the direct loading method of PBT, especially for the esterification reaction, and organic titanium compounds are widely used as catalysts. However, while organic titanium compounds (e.g., titanate esters) exhibit excellent catalytic activity as esterification reaction catalysts, they are subject to hydrolysis by water produced as a by-product during the reaction and decomposition of BG (cyclodehydration). It is easy to generate insoluble foreign substances and reduce the activity as a catalyst. Such problems of generation of insoluble foreign substances and reduction of catalytic activity during the esterification step not only become an impediment to shortening the reaction time, but also significantly reduce the transparency of the reaction product, and even Due to a decrease in polymerization reactivity, the desired degree of polymerization may not be obtained, and in some cases, the polycondensation reaction may "plateau". Furthermore, during the polymer molding process, there may be a decrease in moldability due to insoluble foreign matter. This causes problems such as a decline in the quality of molded products. To solve the problem of insolubilization and deactivation of organic titanium compounds, the esterification reaction rate of organic titanium compounds is 50%.
Improvements in the addition method have been proposed (e.g., Japanese Patent Application Laid-Open No. 49-57092), in which the organic titanium compound is added in the first half and second half, respectively, but the problem of insolubilization and deactivation of organotitanium compounds has not been improved much. There are limits to its effectiveness. In addition, methods such as using a polyhydric alcohol compound and an alkali metal compound together (for example, JP-A-62
-225524 publication), means using an alkanolamine titanate compound as a catalyst (for example, JP-A-62-141022), and means such as using an organic titanium compound and an alkanolamine compound together (for example, JP-A-62-199617) ) have been proposed, but although these methods improve the polymerization reactivity of the polymer to some extent, the problem of insolubilization and deactivation of organotitanium compounds in the esterification stage remains unsolved. This insolubilization and deactivation caused problems such as a decrease in polymer color tone and high viscosity. Therefore, in order to produce PBT with a high degree of polymerization in a short time by the direct loading method, the technical field is concerned with how to solve the problem of insolubilization and deactivation due to hydrolysis of the organotitanium compound catalyst in the esterification step. This was an important issue for consideration. [Problems to be solved by the invention] The problems to be solved by the present invention are to produce PBT by a direct loading method,
In particular, the object is to suppress insolubilization and deactivation of the organotitanium catalyst in the esterification reaction and to shorten the reaction time. Other issues include the generation of insoluble foreign substances, thickening phenomenon due to the formation of branched structures, coloring of the polymer, and deterioration of the physical properties of molded products and fibers by suppressing the insolubilization and deactivation of the organotitanium catalyst in the esterification reaction. The aim is to solve problems such as. [Means for Solving the Problems] The above object of the present invention is to produce polybutylene from a dicarboxylic acid component mainly containing terephthalic acid and a glycol component mainly containing butanediol through an esterification reaction and a polycondensation reaction. When producing terephthalate, this problem can be solved by carrying out the esterification reaction in the presence of a hindered phenol compound and an organic titanium compound. The structure of the present invention will be explained in detail below. First, the hindered phenol compound and organotitanium catalyst used in the esterification reaction of PBT, which is the gist of the present invention, will be described. That is, in the present invention, during the esterification reaction, a hindered phenol compound, that is, a phenol compound having a sterically hindering substituent adjacent to the OH group must be present. Conventionally, it has been known to use this type of hindered phenol compound in the melt polycondensation or solid phase polymerization step of PBT (for example, Japanese Patent Publication No. 7853/1983).
Publication No. 58-34493, etc.). but,
These technologies aim to prevent oxidative decomposition of polymers during melt polycondensation or solid phase polymerization, and hindered phenol compounds are extremely effective in insolubilizing and deactivating organotitanium catalysts during the esterification stage. There is no indication that it acts on Examples of this kind of hindered phenol compounds are hindered phenol compounds represented by the following formulas [] to []. However, X is an integer of 1 to 4, R 1 is an alkyl group having 1 to 20 carbon atoms, and R 2 is an integer of 1 to 4.
【式】
を示す。
具体的には、２，６−ジ−ｔ−ブチルパラクレ
ゾール、３−（３，５−ジ−ｔ−ブチル−４−ヒ
ドロキシフエニル）プロピオン酸、ペンタエリス
リチル−テトラキス［３−（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシフエニル）プロピオネー
ト］、１，６−ヘキサンジオール−ビス［３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフエ
ニル）プロピオネート］、オクタデシル−３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフエ
ニル）プロピオネート、１，３，５−トリメチル
−２，４，６−トリス（３，５−ジ−ｔ−ブチル
−４−ヒドロキシベンジル）ベンゼン、トリエチ
レングリコール−ビス［３−（３−ｔ−ブチル−
５−メチル−４−ヒドロキシフエニル）プロピオ
ネート］などが挙げられ、特にペンタエリスリチ
ル−テトラキス］３−（３，５−ジ−ｔ−ブチル
−４−ヒドロキシフエニル）プロピオネート］、
１，６−ヘキサンジオール−ビス［３−（３，５
−ジ−ｔ−ブチル−４−ヒドロキシフエニル）プ
ロピオネート］などが好ましい。
これらのヒンダードフエノール系化合物は一種
もしくは二種以上を併用することができる。
該ヒンダードフエノール化合物の添加量は、原
料のグリコール成分に対して好ましくは0.001〜
0.1モル％、更に好ましくは0.003〜0.05モル％の
範囲である。添加量が0.001モル％より少ないと
エステル化段階における有機チタン触媒の不溶
化・失活の抑制効果が不充分であり、また0.1モ
ル％より多いと前記効果が飽和するばかりか、ポ
リマの着色傾向があり好ましくない。
ヒンダードフエノール系化合物の添加時期とし
ては、エステル化反応における有機チタン化合物
の不溶化・失活を抑制もしくは防止するためのも
のであるから、有機チタン化合物が存在する反応
系には前記ヒンダードフエノール系化合物を存在
させねばならない。このためにはエステル化反応
触媒として有機チタン化合物を添加する前、また
は同時にヒンダードフエノール系化合物を添加す
る必要がある。また添加に際しては、一括添加、
あるいは分割添加でもよい。これらのヒンダード
フエノール系化合物は必要に応じてエステル化反
応終了以降、重縮合反応前、あるいは重縮合反応
途中に追添加することもできる。
添加方法としては、単独で添加してもよいし、
またBG等の有機溶剤により稀釈し添加しもよ
い。
また本発明における有機チタン化合物の例とし
ては
（R1Ｏ）oTi（OR2）4-o
（ただし、R1，R2は炭素数１〜10の脂肪族、脂
環族、芳香族、炭化水素、ｎは１〜３の数字（少
数を含む）である。）
で表されるチタン酸エステルである。
具体的には、チタン酸のメチルエステル、テト
ラ−ｎ−プロピルエステル、テトラ−ｎ−ブチル
エステル、テトライソプロピルエステル、テトラ
イソブチルエステル、テトラ−tert−ブチルエス
テル、シクロヘキシルエステル、フエニルエステ
ル、ベンジルエステル、トリルエステル、あるい
はこれらの混合エステルなどである。これらのう
ちで特にテトラ−ｎ−プロピルエステル、テトラ
−ｎ−ブチルエステル、テトライソプロピルエス
テルなどが好ましい。これらの有機チタン化合物
は一種もしくは二種以上を併用することができ
る。
該有機チタン化合物の添加量としては、通常生
成ポリマに対して0.005〜0.5重量％、好ましくは
0.01〜0.2重量％の範囲である。添加量が0.005重
量％より少ないと、エステル化反応ないし重縮合
反応触媒としての効果が不充分であり、特にエス
テル化反応においては反応時間が長引くと共に、
テトラヒドロフランの副生量が増加する傾向が認
められる。一方、添加量が0.5重量％より多いと、
触媒効果が飽和状態となるばかりか、生成ポリマ
の透明性が低下したり、物性低下などの欠点が生
じる傾向があり好ましくない。
有機チタン化合物の添加時期としては、エステ
ル化反応前に一括または分割添加してもよい。こ
れらの有機チタン化合物は必要に応じ重縮合反応
触媒として、エステル化反応終了以降重縮合反応
前に一括または分割して添加することもできる。
なお、本発明において、エステル化反応性を更
に高め、かつテトラヒドロフランの副生を一層抑
制するために、モノアリキルスズ化合物、モノア
リールスズ化合物、ジアルキルスズ化合物、ジア
リールスズ化合物、トリアルキルスズ化合物、ト
リアリールスズ化合物、テトラアルキルスズ化合
物などの有機スズ化合物を添加することもでき
る。その場合の添加量は生成ポリマに対して0.01
〜0.5重量％程度が好ましい。
次に、本発明における上記以外の構成について
説明する。
本発明におけるジカルボン酸とは、少なくとも
50モル％がTPAであり、該TPA以外のジカルボ
ン酸としては、例えばイソフタル酸、ナフタリン
ジカルボン酸、ジフエニルジカルボン酸、ジフエ
ニルエタンジカルボン酸、ジフエニルエーテルジ
カルボン酸、セバシン酸、蓚酸、１，４−シクロ
ヘキサンジカルボン酸、ドデカンジオン酸、アジ
ピン酸などの芳香族、脂肪族、脂環族ジカルボン
酸のような共重合成分を50モル％未満を用いるこ
とができる。
また、グリコール成分としては、少なくとも50
モル％がBGであり、該BG以外のグリコール成
分としては、例えばエチレングリコール、プロピ
レングリコール、ジエチレングリコール、トリメ
チレングリコール、１，６−ヘキサンジオール、
シクロヘキサン１，４−ジメタノール、ポリエチ
レングリコール、ポリプロピレングリコール、ポ
リテトラメチレングリコールおよびこれらの変性
物などを50モル％未満の範囲で用いることができ
る。
かかるジカルボン酸及びグリコールとを主たる
出発原料とするエステル化反応は、反応条件とし
て、反応開始時の酸成分に対するグリコール成分
の使用モル比（グリコール／ジカルボン酸）を
2.0以下、好ましくは1.05〜1.8とするのが望まし
い。2.0を越えるとBGの分解による副生テトラヒ
ドロフランが多量に生成し易く、原料コストアツ
プなど経済的な面で好ましくない。
なお、このとき酸成分に対するグリコール成分
の使用モル比を0.4〜1.3としてエステル化反応を
開始し、しかる後、全必要量の残りのグリコール
を追添加してエステル化反応を完結させることも
できる。また、反応温度条件としては180℃〜240
℃の範囲が好ましく、これ以上の高温ではBGの
分解によるテトラヒドロフランの副生量が多くな
る傾向にある。また、この温度はエステル化反応
の開始から完結するまでの間、一定温度で行なつ
てもよく、また反応開始時から随時反応温度を上
昇させる方法であつてもよい。さらに反応圧力条
件としては、通常200〜760mmHgの範囲で行うが、
BGの分解や有機チタン化合物の加水分解などを
抑制する上から、減圧下で行うと効果的である。
なお、このときの反応圧力は弱減圧状態でスター
トし、反応の途中から減圧度を高める方法を採用
してもよい。
エステル化の雰囲気としては、酸素を含まない
不活性気体の雰囲気とすることが好ましい。雰囲
気中に酸素が含まれていると、ヒンダードフエノ
ール系化合物に起因する着色が起こり易くなる。
このようにして得られたエステル化反応生成物
は、引き続き重縮合反応を行うが、その重縮合条
件としては、特に限定されるものではなく、通常
のPBTの製造に用いられる反応条件をそのまま
採用することができる（例えば、温度230℃〜250
℃、圧力１mmHg以下など）。
また、重縮合反応はその一部または全部を固相
で行つてもよい。またその一部または全部を連続
的に行つてもよい。
その他、PBTの諸特性が損なわれない範囲内
で各種の添加剤、例えば艶消剤、蛍光増白剤、安
定剤、紫外線吸収剤、難燃剤、帯電防止剤、結晶
核剤などを適宜添加してもよい。
以下、実施例を挙げて本発明を具体的に説明す
る。
なお、本例中、部とは重量部を意味する。また
固有粘度、ポリマの溶液ヘイズ、溶融粘度（メル
トインデツクス）は次の方法で測定した。
固有粘度
固有粘度はポリマチツプ2.0gを25mlのオルソク
ロロフエノール（OCP）溶媒で加熱溶解し、そ
の後25℃で測定した。
ポリマの溶液ヘイズ
ポリマの溶液ヘイズは、触媒金属化合物の反応
系中での析出により生じる濁り度を表わし、フエ
ノールと四塩化エタン（60：40wt％）を混合溶
媒とし、該溶媒40mlにポリマチツプ5.4gを加熱溶
解し、該ポリマ溶液を30mm石英セルにいれて積分
球式ヘーズメーター（日本精密光学製）で測定し
た。
溶融粘度（メルトインデツクス）
溶融粘度（メルトインデツクス）はメルトイン
デクサー（宝工業製）を使用し、ポリマチツプを
温度250℃で溶融し、荷重2160gをかけて2.0mmφ
のオリフイスから10分間押出し、その重量を測定
した。
実施例１，比較例１
TPA755部、BG696部と第１表に示すテトラ−
ｎ−ブチルチタネート（以下、TBTと略称）お
よびペンタエリスリチル−テトラキス［３−（３，
５−ジ−ｔ−ブチル−４−ヒドロキシフエニル）
プロピオネート］（以下、IR1010と略称）を精留
塔の付いた反応器に仕込み、反応器内をN2ガス
で置換し、180℃から230℃まで徐々に昇温しなが
らエステル化反応を進め、生成する水とテトラヒ
ドロフランを精留塔を経由して留去した。
エステル化を開始してから反応が完結するまで
に要した時間は第１表の通りであつた。
得られた反応生成物をオートクレーブに移し、
第１表に示すようにTBTを添加し、常圧から1.0
mmHg以下まで60分かけて徐々に減圧にし、同時
に245℃まで昇温し、245℃mmHg以下で３時間15
分間、重縮合反応せしめた。
なおこのとき、エステル化反応において
R1010を添加しなかつた場合、並びに重縮合反応
においてのみR1010を添加した場合の例（比較
例）、重縮合反応においてIR1010を追添加した場
合の例（実施例）を示した。
得られたポリマ重合度（固有粘度）、溶液ヘイ
ズを第１表に示した。
これらの結果から明らかなように、反応性向
上、ポリマの溶液ヘイズダウンに関して、本発明
におけるヒンダードフエノール系化合物の効果は
顕著に認められる。
また、本例中、No.２，５およびNo.６，７から明
らかなように、ヒンダードフエノール系化合物を
重縮合開始前に添加しても重縮合反応性の向上効
果は得られず、エステル化反応開始前に添加する
ことではじめて本発明の効果が得られることがわ
かる。
実施例２、比較例２
TPA755部、BG328部と第２表に示すTBT触
媒およびIR1010、さらにジブチルスズオキシド
0.05wt％／ポリマを精留塔の付いた反応器に仕込
み、反応器内をN2ガスで置換し、180℃、550mm
Hgの減圧度でエステル化反応を開始し、徐々に
昇温すると共に、BG206部を連続的に追添加し
た。生成する水とテトラヒドロフランを精留塔を
経由して留去した。エステル化を開始してから反
応が完結するまでに要した時間は第２表に示すと
おりであつた（エステル化反応終了時の温度は
240℃）。
得られた反応生成物をオートクレーブに移し、
第２表に示す有機チタン化合物触媒、および
0.02wt％（対ポリマ）のリン酸を添加し、実施例
１と同じ方法で３時間05分間、重縮合反応せしめ
た。なお、このときエステル化反応において、
IR1010を添加しなかつた場合の例（比較例）を
示した。
得られたポリマの重合度（固有粘度）、溶液ヘ
イズを第２表に示した。
これらの結果からも、反応性向上、ポリマの溶
液ヘイズダウンに関して本発明におけるヒンダー
ドフエノール系化合物の効果は顕著に認められ
る。
実施例 ３
実施例１，No.３において、IR1010の代りに、
第３表に示すヒンダードフエノール系化合物を用
いて反応性向上、ポリマの溶液ヘイズダウンの効
果を調べた。この結果を第３表に示した。
実施例４、比較例３
実施例１，No.３およびNo.７において、重縮合時
間を更に延長して、重縮合反応を進めたときの重
縮合時間に対するポリマの重縮合反応の進行状況
を調べた。その結果を第４表に示した。
これらの結果から、本発明方法にかかるNo.１〜
３はヒンダードフエノール系化合物を添加しない
No.４〜６（比較例）に比べて短時間で高重合度に
到達し、しかもNo.６に見られるような重合反応の
頭打ち現象が起こつていない。
実施例５、比較例４、参考例
実施例１，No.３において、第５表に示すように
IR1010を0.02モル％／BG添加の例、従来技術の
代表的透明化添加剤であるトリメチロールプロパ
ン（以下、TMPと略称）を0.15モル％／BG添加
の例、またエステル化反応時の添加剤を無添加の
例についてエステル化反応を行ない、更に重縮合
時間を変更して種々の重合度のポリマを調整し
た。得られたポリマの重合度（固有粘度）と溶融
粘度（Melt Index）を測定し、それぞれのポリ
マの増粘作用について調べた。
その結果を第５表、第１図に示した。
これらの結果から明らかなように、TMPを添
加したポリマは無添加系ポリマに対して重合度と
溶融粘度の関係に明確な差が現れている。これに
対して本発明におけるヒンダードフエノール系化
合物の代表例であるIR1010を添加したポリマは
添加剤無添加系ポリマと殆ど同じ重合度と溶融粘
度の関係にある。このようにTMPにはポリマに
対して増粘作用があり、一方のIR1010にはその
ような増粘作用が殆どない。[Formula] is shown. Specifically, 2,6-di-t-butyl para-cresol, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid, pentaerythrityl-tetrakis [3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-
(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) Benzene, triethylene glycol-bis[3-(3-t-butyl-
5-methyl-4-hydroxyphenyl)propionate], in particular pentaerythrityl-tetrakis]3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5
-di-t-butyl-4-hydroxyphenyl)propionate] and the like are preferred. These hindered phenol compounds can be used alone or in combination of two or more. The amount of the hindered phenol compound added is preferably 0.001 to 0.001 to the glycol component of the raw material.
The content is 0.1 mol%, more preferably 0.003 to 0.05 mol%. If the amount added is less than 0.001 mol%, the effect of suppressing the insolubilization and deactivation of the organotitanium catalyst in the esterification step will be insufficient, and if it is more than 0.1 mol%, not only will the effect be saturated, but the polymer will tend to color. Yes, it's not good. The purpose of adding the hindered phenol compound is to suppress or prevent the insolubilization and deactivation of the organotitanium compound in the esterification reaction. The compound must be present. For this purpose, it is necessary to add a hindered phenol compound before or at the same time as adding an organic titanium compound as an esterification reaction catalyst. In addition, when adding, bulk addition,
Alternatively, it may be added in portions. These hindered phenol compounds can be added after the esterification reaction is completed, before the polycondensation reaction, or during the polycondensation reaction, if necessary. As for the addition method, it may be added alone,
It may also be added after being diluted with an organic solvent such as BG. Further, examples of the organic titanium compound in the present invention include (R 1 O) o Ti(OR 2 ) 4-o (wherein R 1 and R 2 are aliphatic, alicyclic, aromatic, having 1 to 10 carbon atoms, It is a titanate ester represented by a hydrocarbon, n is a number from 1 to 3 (including decimals). Specifically, titanic acid methyl ester, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, These include tolyl esters and mixed esters thereof. Among these, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester and the like are particularly preferred. These organic titanium compounds can be used alone or in combination of two or more. The amount of the organic titanium compound added is usually 0.005 to 0.5% by weight, preferably 0.005 to 0.5% by weight based on the produced polymer.
It ranges from 0.01 to 0.2% by weight. If the amount added is less than 0.005% by weight, the effect as a catalyst for esterification or polycondensation reactions will be insufficient, and especially in esterification reactions, the reaction time will be prolonged, and
There is a tendency for the amount of tetrahydrofuran by-product to increase. On the other hand, if the amount added is more than 0.5% by weight,
Not only does the catalytic effect reach a saturated state, but the resulting polymer tends to have disadvantages such as decreased transparency and physical properties, which is undesirable. The organic titanium compound may be added all at once or in portions before the esterification reaction. These organic titanium compounds can be added all at once or in portions as a polycondensation reaction catalyst after the esterification reaction is completed and before the polycondensation reaction, if necessary. In addition, in the present invention, in order to further increase the esterification reactivity and further suppress the by-product of tetrahydrofuran, monoalkyltin compounds, monoaryltin compounds, dialkyltin compounds, diaryltin compounds, trialkyltin compounds, triaryltin compounds are used. It is also possible to add organotin compounds such as compounds, tetraalkyltin compounds, etc. In that case, the amount added is 0.01 to the generated polymer.
It is preferably about 0.5% by weight. Next, configurations other than those described above in the present invention will be explained. The dicarboxylic acid in the present invention means at least
50 mol% is TPA, and examples of dicarboxylic acids other than TPA include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenylethanedicarboxylic acid, diphenyl ether dicarboxylic acid, sebacic acid, oxalic acid, 1,4 - Less than 50 mol% of copolymerized components such as aromatic, aliphatic, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, dodecanedioic acid, and adipic acid can be used. In addition, as a glycol component, at least 50
Mol% is BG, and glycol components other than BG include, for example, ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, 1,6-hexanediol,
Cyclohexane 1,4-dimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, modified products thereof, and the like can be used in an amount of less than 50 mol%. In the esterification reaction using dicarboxylic acid and glycol as the main starting materials, the reaction conditions include the molar ratio of the glycol component to the acid component (glycol/dicarboxylic acid) at the start of the reaction.
It is desirable that it be 2.0 or less, preferably 1.05 to 1.8. If it exceeds 2.0, a large amount of by-product tetrahydrofuran is likely to be produced due to the decomposition of BG, which is unfavorable from an economic point of view such as an increase in raw material costs. In addition, at this time, the esterification reaction can be started by setting the molar ratio of the glycol component to the acid component to 0.4 to 1.3, and then the remaining glycol of the total required amount can be further added to complete the esterification reaction. In addition, the reaction temperature conditions are 180°C to 240°C.
The temperature is preferably in the range of 0.degree. C., and at higher temperatures, the amount of tetrahydrofuran as a by-product due to decomposition of BG tends to increase. Further, this temperature may be maintained at a constant temperature from the start of the esterification reaction until its completion, or the reaction temperature may be raised at any time from the start of the reaction. Furthermore, the reaction pressure conditions are usually in the range of 200 to 760 mmHg, but
In order to suppress the decomposition of BG and the hydrolysis of organic titanium compounds, it is effective to perform the reaction under reduced pressure.
Incidentally, the reaction pressure at this time may be started in a slightly reduced pressure state, and a method may be adopted in which the degree of pressure reduction is increased from the middle of the reaction. The esterification atmosphere is preferably an oxygen-free inert gas atmosphere. When oxygen is included in the atmosphere, coloration due to hindered phenol compounds tends to occur. The esterification reaction product obtained in this way is subsequently subjected to a polycondensation reaction, but the polycondensation conditions are not particularly limited, and the reaction conditions used for the production of ordinary PBT are directly adopted. (e.g. temperature 230℃~250℃)
℃, pressure 1 mmHg or less). Further, part or all of the polycondensation reaction may be carried out in a solid phase. Further, part or all of it may be performed continuously. In addition, various additives such as matting agents, optical brighteners, stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, crystal nucleating agents, etc. may be added as appropriate to the extent that the properties of PBT are not impaired. It's okay. The present invention will be specifically described below with reference to Examples. In addition, in this example, parts mean parts by weight. Intrinsic viscosity, polymer solution haze, and melt viscosity (melt index) were measured by the following methods. Intrinsic viscosity Intrinsic viscosity was measured by heating and dissolving 2.0 g of the polymer chip in 25 ml of orthochlorophenol (OCP) solvent, and then measuring it at 25°C. Polymer solution haze Polymer solution haze refers to the turbidity caused by precipitation of a catalytic metal compound in a reaction system.A mixed solvent of phenol and tetrachloroethane (60:40 wt%) is used, and 5.4 g of polymer chips are added to 40 ml of the solvent. was heated and dissolved, and the polymer solution was placed in a 30 mm quartz cell and measured using an integrating sphere haze meter (manufactured by Nippon Seimitsu Kogaku). Melt viscosity (melt index) Melt viscosity (melt index) was determined by melting a polymer chip at a temperature of 250℃ using a melt indexer (manufactured by Takara Kogyo), applying a load of 2160g, and measuring 2.0mmφ.
It was extruded from the orifice for 10 minutes and its weight was measured. Example 1, Comparative Example 1 755 parts of TPA, 696 parts of BG and the tetras shown in Table 1
n-Butyl titanate (hereinafter abbreviated as TBT) and pentaerythrityl-tetrakis [3-(3,
5-di-t-butyl-4-hydroxyphenyl)
Propionate] (hereinafter abbreviated as IR1010) was charged into a reactor equipped with a rectification column, the inside of the reactor was replaced with N 2 gas, and the esterification reaction was proceeded while gradually increasing the temperature from 180°C to 230°C. The produced water and tetrahydrofuran were distilled off via a rectification column. Table 1 shows the time required from the start of esterification to the completion of the reaction. The obtained reaction product was transferred to an autoclave,
Add TBT as shown in Table 1, and from normal pressure to 1.0
Gradually reduce the pressure to below mmHg over 60 minutes, raise the temperature to 245℃ at the same time, and keep it below 245℃mmHg for 3 hours.
The polycondensation reaction was allowed to occur for a few minutes. At this time, in the esterification reaction
Examples are shown in which R1010 is not added, R1010 is added only in the polycondensation reaction (comparative example), and IR1010 is additionally added in the polycondensation reaction (example). Table 1 shows the obtained polymerization degree (intrinsic viscosity) and solution haze. As is clear from these results, the effect of the hindered phenol compound in the present invention in improving the reactivity and reducing the solution haze of the polymer is clearly recognized. In addition, as is clear from Nos. 2 and 5 and Nos. 6 and 7 in this example, even if the hindered phenol compound is added before the start of polycondensation, the effect of improving polycondensation reactivity cannot be obtained. It can be seen that the effects of the present invention can only be obtained by adding it before the start of the esterification reaction. Example 2, Comparative Example 2 755 parts of TPA, 328 parts of BG, the TBT catalyst and IR1010 shown in Table 2, and dibutyltin oxide
Charge 0.05wt%/polymer into a reactor equipped with a rectification column, replace the inside of the reactor with N2 gas, and heat at 180℃, 550mm.
The esterification reaction was started at a reduced pressure of Hg, and while the temperature was gradually raised, 206 parts of BG was continuously added. The produced water and tetrahydrofuran were distilled off via a rectification column. The time required from the start of esterification to the completion of the reaction was as shown in Table 2 (the temperature at the end of the esterification reaction was
240℃). The obtained reaction product was transferred to an autoclave,
The organic titanium compound catalyst shown in Table 2, and
0.02wt% (based on the polymer) of phosphoric acid was added, and a polycondensation reaction was carried out in the same manner as in Example 1 for 3 hours and 5 minutes. At this time, in the esterification reaction,
An example (comparative example) in which IR1010 was not added is shown. Table 2 shows the polymerization degree (intrinsic viscosity) and solution haze of the obtained polymer. From these results as well, the effect of the hindered phenol compound in the present invention in terms of reactivity improvement and polymer solution haze reduction is clearly recognized. Example 3 In Example 1, No. 3, instead of IR1010,
Using the hindered phenol compounds shown in Table 3, the effects of improving reactivity and reducing solution haze of the polymer were investigated. The results are shown in Table 3. Example 4, Comparative Example 3 In Examples 1, No. 3, and No. 7, the progress of the polycondensation reaction of the polymer was compared to the polycondensation time when the polycondensation time was further extended to advance the polycondensation reaction. Examined. The results are shown in Table 4. From these results, No. 1 to 1 according to the method of the present invention
3 does not add hindered phenol compounds
A high degree of polymerization was reached in a shorter time than in Nos. 4 to 6 (comparative examples), and the plateauing phenomenon of the polymerization reaction observed in No. 6 did not occur. Example 5, Comparative Example 4, Reference Example In Example 1, No. 3, as shown in Table 5
Example of adding 0.02 mol%/BG of IR1010, example of adding 0.15 mol%/BG of trimethylolpropane (hereinafter abbreviated as TMP), which is a typical transparent additive in conventional technology, and additives during esterification reaction. An esterification reaction was carried out for examples without the addition of , and polymers with various degrees of polymerization were prepared by changing the polycondensation time. The degree of polymerization (intrinsic viscosity) and melt viscosity (Melt Index) of the obtained polymers were measured, and the thickening effect of each polymer was investigated. The results are shown in Table 5 and Figure 1. As is clear from these results, there appears to be a clear difference in the relationship between polymerization degree and melt viscosity between the TMP-added polymer and the non-additive type polymer. On the other hand, the polymer to which IR1010, which is a typical example of the hindered phenol compound in the present invention, is added has almost the same relationship between polymerization degree and melt viscosity as the additive-free polymer. In this way, TMP has a thickening effect on the polymer, while IR1010 has almost no such thickening effect.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
［発明の効果］
以上述べたように、本発明は直重法による
PBTの製造段階、特にそのエステル化反応系に
おける有機チタン化合物触媒の不溶異物化、失活
問題をヒンダードフエノール系化合物の適用によ
つて解消でき、次のような工業上、極めて大きな
効果を奏する。
(1) エステル化反応の所要時間が従来法（ヒンダ
ードフエノール系化合物不使用の場合）に比較
して大幅に短縮できる。
(2) 有機チタン化合物触媒の加水分解によつて生
成する不溶性異物が減少し、ポリマの溶融透明
性を格段に向上させる。このことは成形加工品
の表面光沢、成形ないし製糸性などの向上を顕
著にする。
(3) 重縮合反応において、より短い時間で所望ど
おりの高重合度（極限粘度；0.8以上）のPBT
が得られる。
(4) 得られたポリマは架橋や増粘現象がなく、高
タフネスの成形品、フイルム、繊維などが得ら
れる。
(5) PBT原料のTPAやBG中には酢酸などの有
機チタン化合物触媒の不溶化・失活を促進する
成分が含有されていることが多いが、本発明の
適用によりそれ等の影響を受けることなく、高
い反応性を維持することができる。
なお、本発明の上記効果が得られる理由は明確
ではないが、本発明におけるヒンダードフエノー
ル系化合物が効率よく有機チタン化合物触媒に配
位して水に強いアルコキサイドを形成するため不
溶化・失活を起こさず、高活性が維持できるもの
と推定される。[Table] [Effects of the invention] As stated above, the present invention is based on the direct loading method.
The problems of insoluble foreign matter formation and deactivation of organotitanium compound catalysts in the PBT production stage, especially in the esterification reaction system, can be solved by applying hindered phenol compounds, and the following industrially significant effects can be achieved. . (1) The time required for the esterification reaction can be significantly shortened compared to the conventional method (when no hindered phenol compound is used). (2) Insoluble foreign matter generated by hydrolysis of the organic titanium compound catalyst is reduced, and the melt transparency of the polymer is significantly improved. This significantly improves the surface gloss of the molded product, as well as the molding and spinning properties. (3) PBT with the desired high degree of polymerization (intrinsic viscosity: 0.8 or more) in a shorter time in polycondensation reactions
is obtained. (4) The resulting polymer has no crosslinking or thickening phenomena, and can be used to produce highly tough molded products, films, fibers, etc. (5) PBT raw materials TPA and BG often contain components such as acetic acid that promote insolubilization and deactivation of organotitanium compound catalysts, but application of the present invention will not be affected by these components. high reactivity can be maintained. Although the reason why the above-mentioned effects of the present invention are obtained is not clear, the hindered phenol compound of the present invention efficiently coordinates with the organic titanium compound catalyst to form a water-resistant alkoxide, which prevents insolubilization and deactivation. It is presumed that high activity can be maintained without this occurring.
第１図は直重法によるPBT製造時において、
添加剤による増粘作用を示す図である。
○……IR1010添加、△……TMP添加、●……
添加剤なし。
Figure 1 shows PBT manufactured by the direct loading method.
It is a figure showing the thickening effect by an additive. ○...IR1010 addition, △...TMP addition, ●...
No additives.
Claims (1)
ブタンジオールを主とするグリコール成分とか
ら、エステル化反応及び重縮合反応を経由してポ
リブチレンテレフタレートを製造するに際し、前
記エステル化反応をヒンダードフエノール系化合
物および有機チタン化合物の存在下で行なうこと
を特徴とする高重合度ポリブチレンテレフタレー
トの製造方法。1 When producing polybutylene terephthalate from a dicarboxylic acid component mainly consisting of terephthalic acid and a glycol component mainly consisting of butanediol through an esterification reaction and a polycondensation reaction, the esterification reaction is performed using a hindered phenol-based A method for producing highly polymerized polybutylene terephthalate, which is carried out in the presence of a compound and an organic titanium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11182188A JPH01282215A (en) | 1988-05-09 | 1988-05-09 | Production of polybutylene terephthalate of high degree of polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11182188A JPH01282215A (en) | 1988-05-09 | 1988-05-09 | Production of polybutylene terephthalate of high degree of polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01282215A JPH01282215A (en) | 1989-11-14 |
| JPH0411574B2 true JPH0411574B2 (en) | 1992-02-28 |
Family
ID=14571003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11182188A Granted JPH01282215A (en) | 1988-05-09 | 1988-05-09 | Production of polybutylene terephthalate of high degree of polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01282215A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940010346B1 (en) * | 1991-06-12 | 1994-10-22 | 한국과학기술연구원 | Process for preparation of polybuthylene therephtalate polymer |
| US6093786A (en) * | 1996-11-27 | 2000-07-25 | Shell Oil Company | Process for preparing polytrimethylene terephthalate |
| ZA9710542B (en) * | 1996-11-27 | 1999-07-23 | Shell Int Research | Modified 1,3-propanediol-based polyesters. |
| JP2008150625A (en) * | 1997-03-31 | 2008-07-03 | Toray Ind Inc | Method for manufacturing polybutylene terephthalate |
| JP2008056874A (en) * | 2006-09-04 | 2008-03-13 | Teijin Fibers Ltd | Method for manufacturing polyester having excellent hue |
| CN109666131B (en) * | 2017-10-17 | 2022-02-01 | 中国石油化工股份有限公司 | Preparation method of polybutylene terephthalate resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4975661A (en) * | 1972-11-24 | 1974-07-22 | ||
| JPS5124695A (en) * | 1974-08-24 | 1976-02-28 | Mitsubishi Chem Ind | Horiesuteruno seizoho |
-
1988
- 1988-05-09 JP JP11182188A patent/JPH01282215A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4975661A (en) * | 1972-11-24 | 1974-07-22 | ||
| JPS5124695A (en) * | 1974-08-24 | 1976-02-28 | Mitsubishi Chem Ind | Horiesuteruno seizoho |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01282215A (en) | 1989-11-14 |
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