JPS62230804A - Fluorine-containing copolymer - Google Patents
Fluorine-containing copolymerInfo
- Publication number
- JPS62230804A JPS62230804A JP29492886A JP29492886A JPS62230804A JP S62230804 A JPS62230804 A JP S62230804A JP 29492886 A JP29492886 A JP 29492886A JP 29492886 A JP29492886 A JP 29492886A JP S62230804 A JPS62230804 A JP S62230804A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- pfave
- branched fluoroalkyl
- perfluorovinyl ether
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 45
- 229910052731 fluorine Inorganic materials 0.000 title claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 7
- 239000011737 fluorine Substances 0.000 title claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 fluoroalkyl perfluorovinyl ether Chemical compound 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BRWSHOSLZPMKII-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanoyl fluoride Chemical compound FC(=O)C(F)(C(F)(F)F)C(F)(F)F BRWSHOSLZPMKII-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 2
- JUTIIYKOQPDNEV-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl 2,2,3,3,4,4,4-heptafluorobutaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)F JUTIIYKOQPDNEV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 101150060820 Pfas gene Proteins 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 2
- 230000009255 platelet function activity Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- CKWDVNHGYYNNTN-UHFFFAOYSA-N 1-ethenoxy-1,1,2,3,3,3-hexafluoro-2-(trifluoromethyl)propane Chemical compound FC(F)(F)C(F)(C(F)(F)F)C(F)(F)OC=C CKWDVNHGYYNNTN-UHFFFAOYSA-N 0.000 description 1
- SYNPRNNJJLRHTI-UHFFFAOYSA-N 2-(hydroxymethyl)butane-1,4-diol Chemical compound OCCC(CO)CO SYNPRNNJJLRHTI-UHFFFAOYSA-N 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DQNJTMHUKISKNY-UHFFFAOYSA-N O=C(C(C(F)(F)F)(OC(C(C(F)(F)F)(C(F)(F)F)F)(F)F)F)F Chemical compound O=C(C(C(F)(F)F)(OC(C(C(F)(F)F)(C(F)(F)F)F)(F)F)F)F DQNJTMHUKISKNY-UHFFFAOYSA-N 0.000 description 1
- IRYBKFGKUNZRSI-UHFFFAOYSA-N Pyrene-1,2-oxide Chemical compound C1=C2C3OC3C=C(C=C3)C2=C2C3=CC=CC2=C1 IRYBKFGKUNZRSI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000005827 chlorofluoro hydrocarbons Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、良成形性を有する高耐熱性の含フツ素共重合
体に関し、更に詳しく言えば、テトラフルオロエチレン
と特定の末端分岐フルオロアルキルパーフルオロビニル
エーテルとの新規な共重合体に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a highly heat-resistant fluorine-containing copolymer with good moldability, and more specifically, to a fluorine-containing copolymer having good moldability and a specific terminal branched fluoroalkyl copolymer. This invention relates to a novel copolymer with perfluorovinyl ether.
［従来の技術］
従来テトラフルオロエチレン（以下、ＴＦＥと略記する
）とフルオロアルキルパーフルオロビニルエーテル（以
下、ＰＦＡＶＥと略記する）からなる共重合体において
、ＰＦＡＶＥとシテ、ＣＦ２−０Ｆ（ＯＣＦ２ＣＦＸ）
１０ＣＦ２ＣＦｚＸ （ｎ ≧１．Ｘ＝Ｆ。[Prior Art] In the conventional copolymer consisting of tetrafluoroethylene (hereinafter abbreviated as TFE) and fluoroalkyl perfluorovinyl ether (hereinafter abbreviated as PFAVE), PFAVE and shite, CF2-0F (OCF2CFX)
10CF2CFzX (n≧1.X=F.
ＣＩ、Ｈ，ＣＦ３．ＣＦ２Ｘ）、 ＣＦ２５ｌＣＦＯ（
ＣＦ２）ｎｃＦ２Ｘ （ｎ＝ Ｏ〜？、 Ｘ＝Ｆ、Ｈ）
、 ＣＦ２＝（１：ＦＯＣＦ２０Ｆ２（ＯＣＦ２）ｎＯ
ＣＦ３（ｎ＝１〜５）などが知られている（特公昭４２
−１８３４０ 。CI, H, CF3. CF2X), CF25lCFO(
CF2) ncF2X (n= O~?, X=F, H)
, CF2=(1:FOCF20F2(OCF2)nO
CF3 (n=1 to 5) etc. are known (Special Publication Act 1977).
-18340.
特公昭４８−２２２３． 特開昭４９−５３９８４
、特開昭５８−１８９２１０などを参照）。Special Publication Showa 48-2223. Japanese Patent Publication No. 49-53984
, JP-A-58-189210, etc.).
而して、ＰＦＡＶＥは高価であり、目的の特は、より少
量が望ましい。しかしながら、従来技術において最も一
般的に採用されているＰＦＡＶＥであるパーフルオロプ
ロピルパーフルオロビニルエーテル（以下、ＰＰＶＥと
略記する）では、その含有量が１〜２モル％程度の少量
の場合には、例えば１００ｋｇ／ ｃｍ２程度というよ
うな高温強度の達成が困難であった。Therefore, PFAVE is expensive and, depending on the purpose, a smaller amount is desirable. However, perfluoropropyl perfluorovinylether (hereinafter abbreviated as PPVE), which is the most commonly used PFAVE in the prior art, has a small content of about 1 to 2 mol%, for example. It was difficult to achieve high temperature strength of about 100 kg/cm2.
一方、ＴＦＥとＰＦＡＶＥの共重合体は、その特性を生
かして、電子部品など高精度の射出あるいは押出し成形
品の素材として使用される場合には、適当な分子量範囲
などに甚くより優れた成形性が必要とされる。しかしな
がら、従来技術におけるＰＰＶＥでは、成形性を高める
ための適当な分子量範囲の共重合体とすると、一般的に
は高温特性がさらに低下してしまう傾向が認められる。On the other hand, when copolymers of TFE and PFAVE are used as materials for high-precision injection or extrusion molded products such as electronic parts, they can be used in a suitable molecular weight range and have extremely superior molding properties. sexuality is required. However, in conventional PPVE, when a copolymer is used in an appropriate molecular weight range to improve moldability, it is generally recognized that high-temperature properties tend to further deteriorate.
以上ノ如く、従来のＴＦＥ／ＰＦＡＶＥ共重合体におい
ては、成形性と高温特性の両面について満足し得るもの
は見出されていない。As mentioned above, no conventional TFE/PFAVE copolymer has been found that satisfies both moldability and high-temperature properties.
［発明の解決しようとする問題点］
本発明の目的は、前記のごとき従来技術における問題点
を解消しようとするものであり、少量のＰＦＡＶＥで目
的の物性を持つ共重合体を与え、さらに優れた成形性と
高温特性を共有する共重合体を提供することにある。[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned problems in the prior art, and to provide a copolymer with desired physical properties using a small amount of PFAVE, and to achieve even better properties. The object of the present invention is to provide a copolymer that shares good moldability and high-temperature properties.
［発明を解決するための手段］
本発明者は、前述の目的のもとに、ＴＦＥと各種ＰＦＡ
ＶＥとの共重合体について、種々の研究、検討を重ねた
結果、次の如き興味深い知見を得るに至った。すなわち
、ＰＦＡＶＥについては米国特許第３，３２１，５３２
号明細書などに、またＴＦＥ／ＰＦＡＶＥ共重合体につ
いては同米国特許明細書や前記の特公昭４２−１８３４
０ 。[Means for Solving the Invention] For the above-mentioned purpose, the present inventor has developed TFE and various PFAs.
As a result of various studies and examinations regarding copolymers with VE, the following interesting findings have been obtained. That is, U.S. Patent No. 3,321,532 for PFAVE.
In addition, regarding the TFE/PFAVE copolymer, the same US patent specification and the above-mentioned Japanese Patent Publication No. 42-1834
0.
同４８−２２２３号公報などに、それぞれ種々のものが
開示されているが、具体的に挙げられたＴＦＥ／ＰＰＶ
Ｅ共重合体などには、前述の如き問題点が認められる。Various types of TFE/PPV are disclosed in Japanese Patent Publication No. 48-2223, etc., but specifically mentioned TFE/PPV
E copolymers and the like have the above-mentioned problems.
而して、本発明者は、Ｐ Ｆ Ａ Ｖ Ｅ 、！： Ｌ
テＣＦ２＝ＣＦＯＣＦ２ＣＦ−ＣＦ３ （１）如き八Ｆ
３
末端分岐フルオロアルキル基を持ったパーフルオロビニ
ルエーテルを採用することにより、比較的少量の使用で
優れた高温強度を達成可能であるという事実を見出した
ものである。さらに、上記の如き特定の末端分岐ＰＦＡ
ＶＥを採用すると、成形性のより好適な分子量範囲にし
ても、良好な高温強度を保持し得るという事実をも見出
したものである。Therefore, the inventor of the present invention, P F A VE,! : L
TeCF2=CFOCF2CF-CF3 (1) Like 8F
3. By employing perfluorovinyl ether having a terminal branched fluoroalkyl group, it has been discovered that excellent high-temperature strength can be achieved with a relatively small amount of use. Furthermore, certain terminally branched PFAs as described above
It has also been discovered that when VE is employed, good high-temperature strength can be maintained even if the molecular weight is set to a more suitable molecular weight range for moldability.
なお、後述の比較例からも明らかなように、末端でない
部分に分岐を有する
ＣＦ２ ＝ＣＦＯＣＦ２０ＦＯＣ３Ｆ？ （以下、Ｐ
ＨＶＥと略記す占Ｆ３
る）の如きＰＦＡＶＥの場合には、本発明における効果
は認められない。Note that, as is clear from the comparative example described later, CF2 having a branch at a portion other than the terminal = CFOCF20FOC3F? (Hereinafter, P
In the case of PFAVE such as F3 (abbreviated as HVE), the effect of the present invention is not observed.
かくして、本発明は、上記知見に基いて完成されたもの
であり、テトラフルオロエチレンと中のｎは０又は １
〜３の整数を示す）で表わされる末端分岐フルオロアル
キルパーフルオロビニルエーテルとの共重合体であり、
上記末端分岐フルオロアルキルパーフルオロビニルエー
テルの含有量が０．５〜３モル％であり、後記に定義す
る容量流速が０．５＋ａｍ３／秒以上であることを特徴
とする含フツ素共重合体を新規に提供するものである。Thus, the present invention was completed based on the above findings, and consists of tetrafluoroethylene and n in 0 or 1.
It is a copolymer with a terminal branched fluoroalkyl perfluorovinyl ether represented by
A novel fluorine-containing copolymer characterized in that the content of the terminal branched fluoroalkyl perfluorovinyl ether is 0.5 to 3 mol%, and the volumetric flow rate as defined below is 0.5+am3/sec or more. It is provided to
本発明においては、ＰＦＡＶＥとして、末（ｎ＝０〜３
）を使用することが重要であり、特に高温強度の保持の
理由で、ｎ＝０のパーフルオロイソブチルパーフルオロ
ビニルエーテルＣＦ２ ＝ ＣＦＯＣ；Ｆ２ＣＦ−ＣＦ
３（以下、ＰＩＢＶＥ、！−略記晶
する）を使用することが好ましい。In the present invention, as PFAVE,
) is important, especially for reasons of high temperature strength retention, to use perfluoroisobutyl perfluorovinyl ether CF2 = CFOC; F2CF-CF with n = 0.
3 (hereinafter referred to as PIBVE, !-abbreviation) is preferably used.
本発明において、特定の末端分岐ＰＦＡＶＥの含有量は
、０．５〜３モル％、特に １〜２モル％とすることが
、高温強度の保持及び製造コストの低減の理由で望まし
い。In the present invention, the content of the specific terminally branched PFAVE is desirably 0.5 to 3 mol%, particularly 1 to 2 mol%, in order to maintain high temperature strength and reduce manufacturing costs.
而して本発明のＴＦＥ／特定の末端分岐ＰＦＡＶＥ共重
合体は、良好な成形性の理由で、適当な分子量範囲にあ
ることが望ましく、通常は容量流速０．５ｍｍ３／秒以
上、好ましくは１〜５０ｍｌ１１３／秒、特に２〜３０
ｍｔａ３／秒程度を有することが望ましい。容量流速
が余りに小さすぎると、射出成形や押出成形などの加熱
溶融成形性に難点が生じ、また余りに大きな容量流速で
は、耐熱性などに難点を生ずると共に、高温強度につい
ても不利となる。Therefore, the TFE/specific terminal branched PFAVE copolymer of the present invention desirably has a molecular weight in an appropriate range for good moldability, and usually has a volumetric flow rate of 0.5 mm3/sec or more, preferably 1 ~50ml113/sec, especially 2-30
It is desirable to have about mta3/sec. If the volumetric flow rate is too low, there will be difficulties in heat-melt moldability in injection molding, extrusion molding, etc., and if the volumetric flow rate is too large, it will be disadvantageous in terms of heat resistance, etc., and will also be disadvantageous in terms of high-temperature strength.
本発明において、共重合体の重合方法としては、特に限
定されることなく、従来より公知乃至周知の方法が種々
採用可能であり、例えば、溶液重合、懸濁重合、乳化重
合のいずれの方法も使用出来るが、木共重合体の主要用
途において重金属の混入をさける必要から、溶液重合及
び懸濁重合が望ましい。溶液重合における溶剤は、七ツ
マ−及び重合体との親和性を高める必要から、フルオロ
炭化水素またはクロロフルオロ炭化水素が望ましい。か
かる好適な溶剤としては、 ＣＣｌ２ ＦＣＧＩＦ２
（Ｒ−１１３） 、ＣＧＩｈＣＣＩｈ （Ｒ−１１４）
。In the present invention, the method of polymerizing the copolymer is not particularly limited, and various conventionally known or well-known methods can be employed.For example, any method such as solution polymerization, suspension polymerization, or emulsion polymerization can be used. Although it can be used, solution polymerization and suspension polymerization are preferred because it is necessary to avoid contamination with heavy metals in the main uses of wood copolymers. The solvent used in the solution polymerization is preferably a fluorohydrocarbon or a chlorofluorohydrocarbon, since it is necessary to increase the affinity with the polymer. Such suitable solvents include: CCl2 FCGIF2
(R-113), CGIhCCIh (R-114)
.
ＣＧ１３Ｆ（Ｒ−１１）等が例示される。また、懸濁重
合における媒体は、水と有機溶剤の混合媒体とすること
が望ましく、有機溶剤の割合は５〜９０玉量％程度、特
にｌＯ〜７０ｇ１量％が好ましい。ここにおける有機溶
剤としては、前述のＲ−１１３゜Ｒ−１１４，Ｒ−１１
３が例示される。Examples include CG13F (R-11). The medium for suspension polymerization is preferably a mixed medium of water and an organic solvent, and the proportion of the organic solvent is preferably about 5 to 90% by weight, particularly 1O to 70g1% by weight. As the organic solvent here, the above-mentioned R-113゜R-114, R-11
3 is exemplified.
好適な重合方法における重合開始剤としては、油溶性の
パーオキサイドが広範囲にわたって使用出来るが、耐熱
性の保持の理由から、水素を含まないあるいは少量含む
フルオロアルキル基含有パーオキサイドの使用が好まし
い。As a polymerization initiator in a suitable polymerization method, a wide range of oil-soluble peroxides can be used, but for the reason of maintaining heat resistance, it is preferable to use a fluoroalkyl group-containing peroxide that does not contain hydrogen or contains a small amount of hydrogen.
好適なパーオキサイドとしては、［Ｃ３Ｆ７ Ｃ００）
２゜［ＣＩＣＦ２ＣＦｚＣＯＯ）２などが例示される。Suitable peroxides include [C3F7 C00]
An example is 2°[CICF2CFzCOO)2.
また、分子量調節のための連鎖移動剤の添加も採用可能
であり、例えば四塩化炭素、ｎ−ペンタン、ｎ−ヘキサ
ン、インペンタン、トリクロロフルオロメタン、メタノ
ールの如き連鎖移動剤を使用することができる。It is also possible to add a chain transfer agent to control the molecular weight; for example, chain transfer agents such as carbon tetrachloride, n-pentane, n-hexane, impentane, trichlorofluoromethane, and methanol can be used. .
上記の如き重合方法の操作１条件などについても、特に
限定がなく、広範囲にわたって採用され得るが、好適な
実施態様については、後述の具体例において例示される
。The operating conditions of the polymerization method as described above are not particularly limited and may be adopted over a wide range of conditions, but preferred embodiments will be exemplified in the specific examples below.
［作用］
定のＰＦＡＶＥを用いた共重合体が、従来のＰＦＡＶＥ
の場合より高温特性が優れている作用機構は必ずしも明
確でないが、末端が分岐したバルキーな側鎖の導入によ
り剛性が高められ、高温特性の向上の効果をもたらして
いると考えられる。かかる説明は、本発明の理解の助け
に役立てるものであり、本発明を何ら限定するものでな
いことは勿論である。[Action] A copolymer using a certain amount of PFAVE
Although the mechanism by which the high-temperature properties are superior to that of the case of 2 is not necessarily clear, it is thought that the introduction of bulky side chains with branched terminals increases rigidity, resulting in the effect of improving high-temperature properties. It goes without saying that such explanations are helpful in understanding the present invention and do not limit the present invention in any way.
［実施例］
次に試験例、実施例および比較例を示し、本発明をさら
に具体的に説明する。なお、融点、共重合体組成、容量
流速および高温（２５０°Ｃ）での引張破断強度、伸度
の測定は、次の方法で行なった。[Example] Next, test examples, examples, and comparative examples will be shown to further specifically explain the present invention. The melting point, copolymer composition, volume flow rate, tensile strength at break at high temperature (250°C), and elongation were measured by the following methods.
融点：
島律製作所製ＤＴ−３０型を用い、昇温速度ｌＯ°Ｃ／
分で室温から昇温し、融解曲線の最大イｌ／ｊを融点と
した。Melting point: Using DT-30 model manufactured by Shima Ritsu Seisakusho, heating rate 10°C/
The temperature was raised from room temperature in minutes, and the maximum l/j of the melting curve was taken as the melting point.
共重合体組成：
ＴＦＥとＰＰＶＥの共重合体における
ＰＰＶＥの含有量の測定法は、特公昭４８−２２２３に
知られており、ＩＲ分析の結果から下記の式で算出する
。Copolymer composition: A method for measuring the content of PPVE in a copolymer of TFE and PPVE is known in Japanese Patent Publication No. 48-2223, and is calculated using the following formula from the results of IR analysis.
本発明においても、ＴＦＥ／ＰＰＶＥ共重合体はこの方
法で定量し、またＴＥＥ／ＰＩＢＶＥ共重合体及びＴＦ
Ｅ／ＰＨＶＥ共重合体については、この方法に帛拠する
方法で測定した。In the present invention, TFE/PPVE copolymer is also quantified by this method, and TEE/PIBVE copolymer and TF
The E/PHVE copolymer was measured by a method based on this method.
容量流速：
本明細ど中において、容量流速は共重合体の分子量の目
安となる値であり、以下の通り定義される。Volumetric flow rate: Throughout this specification, the volumetric flow rate is a value that serves as a guideline for the molecular weight of the copolymer, and is defined as follows.
島律製作所製高化式フローテスターを用い、共重合体を
内径９．５ｍ＋ａのシリンダーに入れ、温度３８０°Ｃ
で５分間保った後、７ｋｇのピストン荷重下に内径２．
１ｍｍ、長さ ８層層のオリフィスを通して押し出し、
このときの押出速度（ｍ層３／秒）を求めた。Using a Koka type flow tester made by Shima Ritsu Seisakusho, the copolymer was placed in a cylinder with an inner diameter of 9.5 m + a, and the temperature was 380°C.
After holding for 5 minutes at 7 kg, the inner diameter was 2.
Extruded through an orifice of 1 mm long and 8 layers,
The extrusion speed (m layers 3/sec) at this time was determined.
高温（２５０℃）での引張破断強度・伸度：Ａ Ｓ Ｔ
Ｍ −１４５７−８２Ｔに従い、ミクロダンヘルヲ用
いて厚み０．５鵬層のサンプルをつくり、２５０°Ｃで
３回引張試験を行ない、引張破断強度及び伸度を求めた
。Tensile breaking strength and elongation at high temperature (250°C): A S T
In accordance with M-1457-82T, a sample with a thickness of 0.5 layers was prepared using Micro Dangel, and a tensile test was conducted three times at 250°C to determine the tensile strength at break and elongation.
参考例１
［パーフルオロイソブチリルフロリドの合成］パーフル
オロイソブチリルフロリドは既知の方法（Ｊ、Ａｍ、Ｃ
ｈｅｍ、Ｓｏｃ、、 ８４．４２７５．（１９Ｂ２））
により合成した。すなわち、ヘキサフルオロプロピレン
９５ｇとカルボニルフロリド７５ｇをアセトニトリル中
、ＣｓＦ存在下に１００℃で５時間反応させ、蒸留によ
りパーフルオロイソブチリルフロリド１５０ｇ（８０％
）を得た。Reference Example 1 [Synthesis of perfluoroisobutyryl fluoride] Perfluoroisobutyryl fluoride was synthesized by a known method (J, Am, C
hem, Soc,, 84.4275. (19B2))
It was synthesized by That is, 95 g of hexafluoropropylene and 75 g of carbonyl fluoride were reacted in acetonitrile in the presence of CsF at 100°C for 5 hours, and 150 g of perfluoroisobutyryl fluoride (80%
) was obtained.
［パーフルオロ−２，５−ジメチル−３−オキサヘキサ
ノイルフロリドの合成］
パーフルオロイソブチリルフロリド１４７ｇ、ＣｓＦ
８．９ｇ、ジグライム８２ｇの混合物中に、ヘキ’ｔ−
ｙル才ロプロ“ピレンオキシドを内圧がＩｋｇ／ｃｍ２
になるように０〜５℃で加え（全体で１７０ｇ） 、反
応終了後、蒸留によりパーフルオロ−２，５−ジメチル
−３−オキサヘキサノイルフロリド１０４ｇ（４０％）
及びパーフルオロ−２，５，８−トリメチル−３，８−
ジオキサノナノイルフロリド７７ｇ（２ｔｇ）を得た。[Synthesis of perfluoro-2,5-dimethyl-3-oxahexanoyl fluoride] 147 g of perfluoroisobutyryl fluoride, CsF
In a mixture of 8.9 g of diglyme and 82 g of diglyme,
The internal pressure of pyrene oxide is Ikg/cm2.
(170 g in total), and after the reaction was completed, 104 g (40%) of perfluoro-2,5-dimethyl-3-oxahexanoyl fluoride was obtained by distillation.
and perfluoro-2,5,8-trimethyl-3,8-
77 g (2 tg) of dioxanonanoyl fluoride was obtained.
［パーフルオロイソブチルビニルエーテル（ＰＩ ＢＹ
Ｅ）の合成］
パーフルオロ−２，５−ジメチル−３−オキサノイルフ
ロリドを対応するカリウム塩にし、しかる後、２００℃
で熱分解を行い、パーフルオロイソブチルビニルエーテ
ルを得た。[Perfluoroisobutyl vinyl ether (PI BY
Synthesis of E)] Convert perfluoro-2,5-dimethyl-3-oxanoyl fluoride into the corresponding potassium salt, and then heat at 200°C.
Thermal decomposition was carried out to obtain perfluoroisobutyl vinyl ether.
（ｂｐ ８２℃、８５％）
実施例１
脱気した容量２６０ＩＩＱ及び攪拌機を有するステンレ
ス酸の圧力容器に、１，２．２４リクロロ−１，１，２
−トリフルオロエタン（Ｒ−１１３） ３４８ｇ、パー
フルオロイソブチルパーフルオロビニルエーテ／ｌ／
（Ｐ Ｉ ＢＶＥ） ５．１ｇ及びメタ／ −ル０．０
８５ｇを仕込んだ、この混合物を５０°Ｃまで加熱し、
圧力が３．１５ｋｇ／ｃｍ２Ｇになるまでテトラブルオ
ロエチレン（Ｔ Ｆ Ｅ）を添加した０次いで、パーフ
ルオロブチリルパーオキサイド開始剤０．０３４ｇをＲ
−１１３の約１％溶液としてオートクレーブ中に圧入し
た。ＴＦＥを逐次添加することによって操作圧力を維持
し、反応時間６０分後にＴＦＨの供給を停止し１反応容
器より重合溶液を取り出した６次いで、グラスフィルタ
ーで濾過し、洗浄後１５０°Ｃで１６時間乾燥した。こ
の乾燥共重合体は２５．３ｇであった。共重合体の物性
測定結果を下記の表−１に示す。(bp 82°C, 85%) Example 1 In a stainless acid pressure vessel with degassed volume 260 IIQ and a stirrer, 1,2.24lichloro-1,1,2
-Trifluoroethane (R-113) 348g, perfluoroisobutyl perfluorovinylethe/l/
(PI BVE) 5.1g and m/-ol 0.0
85g of this mixture was heated to 50°C,
Then, 0.034 g of perfluorobutyryl peroxide initiator was added to R until the pressure was 3.15 kg/cm2G.
-113 was pressed into an autoclave as an approximately 1% solution. The operating pressure was maintained by sequentially adding TFE, and after 60 minutes of reaction time, the supply of TFH was stopped, and the polymerization solution was taken out from the reaction vessel.6 Then, it was filtered with a glass filter, and after washing, it was heated at 150 °C for 16 hours. Dry. This dry copolymer weighed 25.3 g. The results of measuring the physical properties of the copolymer are shown in Table 1 below.
実施例２
メタノール０．１７ｇを仕込む以外は、実施例１と同様
な手順を繰返して、共重合体２４．８ｇを得た。結果を
下記の表−１に示す。Example 2 The same procedure as in Example 1 was repeated except that 0.17 g of methanol was added to obtain 24.8 g of a copolymer. The results are shown in Table 1 below.
実施例３
実施例１で用いた圧力容器に、脱酸素脱ミネラル水１１
２ｇ、 １，２．２−トリクロロ−１，１，２−トリフ
ルオロエタン（Ｒ−１１３） ８９ｇ、パーフルオロイ
ソブチルパーフルオロビニルエーテル（ＰＩＢＶＥ）
８．８ｇ及びメタノール１１３．５ｇを仕込み、この混
合物を５０″Ｃまで昇温し、圧力が１３．４ｋｇ／ｃｍ
２Ｇになるまでテトラフルオロエチレン（ＴＦＥ）を仕
込んだ。Example 3 Deoxygenated demineralized water 11 was added to the pressure vessel used in Example 1.
2g, 1,2.2-trichloro-1,1,2-trifluoroethane (R-113) 89g, perfluoroisobutyl perfluorovinylether (PIBVE)
8.8g and 113.5g of methanol were charged, and the mixture was heated to 50"C and the pressure was 13.4kg/cm.
Tetrafluoroethylene (TFE) was charged until it reached 2G.
次いで、重合開始剤パーフルオロブチリルパーオキサイ
ドＣＧ３ Ｆ７ Ｃ００）２５重量％Ｒ−１１３溶液を
ＩＩＩＱ添加した０反応の進行と共に圧力が降下するの
でＴＦＥを追加供給して重合圧力を維持した。途中、開
始剤溶液４ｔｓＱを４回にわけて添加した０重合時間１
８０分後にＴＦＥの供給を停止し、未反応上ツマ−をパ
ージし圧力容器から重合溶液を取り出した。次いで水洗
、濾過、乾燥して共重合体２８．８ｇを得た。共重合体
の物性測定結果を下記の表−１に示す。Next, a polymerization initiator perfluorobutyryl peroxide CG3 F7 C00) 25% by weight R-113 solution was added to IIIQ. As the reaction progressed, the pressure decreased, so TFE was additionally supplied to maintain the polymerization pressure. 0 Polymerization time 1 Added initiator solution 4tsQ in 4 parts during the process
After 80 minutes, the supply of TFE was stopped, the unreacted upper part was purged, and the polymerization solution was taken out from the pressure vessel. The copolymer was then washed with water, filtered, and dried to obtain 28.8 g of a copolymer. The results of measuring the physical properties of the copolymer are shown in Table 1 below.
比較例１
ビニルエーテルとしてパーフルオロプロピルビニルＸ−
−フル（ＰＰＶＥ）４．２９ｇを用い、メタノール０．
１２ｇを用いる以外は、実施例１と同様な手順を繰返し
て共重合体２８．９ｇを得た。結果を下記の表−１に示
す。Comparative Example 1 Perfluoropropylvinyl X- as vinyl ether
- Using 4.29 g of PPVE, 0.0 g of methanol.
The same procedure as in Example 1 was repeated except that 12 g was used to obtain 28.9 g of a copolymer. The results are shown in Table 1 below.
比較例２
メタノール０． ｔａｇを仕込む以外は、比較例１と同
様な手順を繰返して共重合体２８．０ｇを得た。結果を
下記の表−１に示す。Comparative Example 2 Methanol 0. The same procedure as in Comparative Example 1 was repeated except for adding tag to obtain 28.0 g of a copolymer. The results are shown in Table 1 below.
比較例３
ビニルエーテルとしてパーフルオロ−２−ｎ−プロポキ
シプロビルパーフルオロビニルエーテル（ＰＨＶＥ）７
．０ｇを用い、メタノール０．１２ｇを用いる以外は、
実施例１と同様な手順を繰返して共重合体２４．８ｇを
得た。結果を下記の表−１に示す。Comparative Example 3 Perfluoro-2-n-propoxypropyl perfluorovinyl ether (PHVE) 7 as vinyl ether
．． Except using 0g and 0.12g of methanol,
The same procedure as in Example 1 was repeated to obtain 24.8 g of a copolymer. The results are shown in Table 1 below.
［発明の効果］
本発明の含フツ素共重合体は、従来知られているＰＰＶ
Ｅなどの場合より少ない量で、目標の１００ｋｇ／ｃｍ
２近い強度を達成することが出来る。さらに本共重合体
の用途から要求される良成形領域（容量流速１３ｍｍ３
／秒以上）においても、従来のＰＰＶＥなどの場合より
高い強度を保持する。[Effects of the Invention] The fluorine-containing copolymer of the present invention can be used in combination with conventionally known PPV
Achieving the target of 100kg/cm with a smaller amount than in cases such as E.
It is possible to achieve an intensity close to 2. Furthermore, the good molding area required for the use of this copolymer (volume flow rate 13 mm3)
/second), it maintains higher strength than conventional PPVE.
従って、電子機器部品、電気機器部品、電線、化学工業
用部品等の高耐熱、高耐久性の要求される広範囲の用途
において有用である。Therefore, it is useful in a wide range of applications requiring high heat resistance and high durability, such as electronic equipment parts, electrical equipment parts, electric wires, and chemical industry parts.
Claims (1)
分岐フルオロアルキルパーフルオロビニルエーテルとの
共重合体であり、上記末端分岐フルオロアルキルパーフ
ルオロビニルエーテルの含有量が０．５〜３モル％であ
り、本文中に定義する容量流速が０．５ｍｍ＾３／秒以
上であることを特徴とする含フッ素共重合体。 ２、末端分岐フルオロアルキルパーフルオロビニルエー
テルが▲数式、化学式、表等があります▼である特 許請求の範囲第１項記載の含フッ素共重合体。[Claims] 1. Tetrafluoroethylene and a terminally branched fluoroalkyl perfluoroethylene represented by the formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (where n in the formula represents 0 or an integer from 1 to 3) It is a copolymer with vinyl ether, the content of the terminal branched fluoroalkyl perfluorovinyl ether is 0.5 to 3 mol%, and the volumetric flow rate as defined in the text is 0.5 mm^3/sec or more. A fluorine-containing copolymer characterized by: 2. The fluorine-containing copolymer according to claim 1, wherein the terminal branched fluoroalkyl perfluorovinyl ether is ▲a numerical formula, a chemical formula, a table, etc.▼.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-282773 | 1985-12-18 | ||
| JP28277385 | 1985-12-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62230804A true JPS62230804A (en) | 1987-10-09 |
Family
ID=17656885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29492886A Pending JPS62230804A (en) | 1985-12-18 | 1986-12-12 | Fluorine-containing copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62230804A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931511A (en) * | 1987-09-17 | 1990-06-05 | Daikin Industries, Ltd. | Cross-linkable coating composition |
| US5576402A (en) * | 1993-09-25 | 1996-11-19 | Hoechst Aktiengesellschaft | Process for the preparation of a modified polytetrafluoroethylene and its use |
| JP2013060412A (en) * | 2011-08-22 | 2013-04-04 | Unimatec Co Ltd | Method of manufacturing perfluoroalkyl vinyl ether |
| JP2013177574A (en) * | 2012-02-01 | 2013-09-09 | Daikin Industries Ltd | Sealing material |
| JP2015193615A (en) * | 2014-03-26 | 2015-11-05 | 株式会社豊田中央研究所 | Perfluorovinyl ether monomer |
| WO2018221518A1 (en) * | 2017-06-02 | 2018-12-06 | Ａｇｃ株式会社 | Modified polytetrafluoroethylene and method for producing same |
-
1986
- 1986-12-12 JP JP29492886A patent/JPS62230804A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931511A (en) * | 1987-09-17 | 1990-06-05 | Daikin Industries, Ltd. | Cross-linkable coating composition |
| US5576402A (en) * | 1993-09-25 | 1996-11-19 | Hoechst Aktiengesellschaft | Process for the preparation of a modified polytetrafluoroethylene and its use |
| JP2013060412A (en) * | 2011-08-22 | 2013-04-04 | Unimatec Co Ltd | Method of manufacturing perfluoroalkyl vinyl ether |
| JP2013177574A (en) * | 2012-02-01 | 2013-09-09 | Daikin Industries Ltd | Sealing material |
| JP2015193615A (en) * | 2014-03-26 | 2015-11-05 | 株式会社豊田中央研究所 | Perfluorovinyl ether monomer |
| WO2018221518A1 (en) * | 2017-06-02 | 2018-12-06 | Ａｇｃ株式会社 | Modified polytetrafluoroethylene and method for producing same |
| CN110662778A (en) * | 2017-06-02 | 2020-01-07 | Ａｇｃ株式会社 | Modified polytetrafluoroethylene and process for producing the same |
| CN110662778B (en) * | 2017-06-02 | 2021-08-17 | Ａｇｃ株式会社 | Modified polytetrafluoroethylene and process for producing the same |
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