JPS62230803A - Flame-retardant resin having good moldability - Google Patents
Flame-retardant resin having good moldabilityInfo
- Publication number
- JPS62230803A JPS62230803A JP14968886A JP14968886A JPS62230803A JP S62230803 A JPS62230803 A JP S62230803A JP 14968886 A JP14968886 A JP 14968886A JP 14968886 A JP14968886 A JP 14968886A JP S62230803 A JPS62230803 A JP S62230803A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- flame
- thermal decomposition
- mol
- ethylene
- 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.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 14
- 229920005989 resin Polymers 0.000 title claims abstract description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000003063 flame retardant Substances 0.000 title claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 239000011737 fluorine Substances 0.000 claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 abstract description 8
- 238000000465 moulding Methods 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- 229940029284 trichlorofluoromethane Drugs 0.000 description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical group CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 239000004340 Chloropentafluoroethane Substances 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KGMXPXPXPAAUMD-UHFFFAOYSA-N propane;dihydrochloride Chemical compound Cl.Cl.CCC KGMXPXPXPAAUMD-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、良成形性を有する難燃性樹脂に関し、更に詳
しく言えば、テトラフルオロエチレン、クロロトリフル
オロエチレン及びエチレンが共重合した特定の含フッ素
共重合体からなる辷記難燃性樹脂に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a flame-retardant resin having good moldability, and more specifically, to a flame-retardant resin having good moldability. The present invention relates to a flame-retardant resin made of a fluorine-containing copolymer.
［従来の技術］
近年、プレナム電線用被覆材、防火材用などとして、高
い酸素指数、低発煙性、低ドリップ性を示す難燃性樹脂
が注目されている。このような特性を有する樹脂の一つ
として、クロロトリフルオロエチレン（以下、ＣＴＦＥ
と略記する）とエチレン（以下、ＥＴと略記する）の含
フッ素共重合体が知られている０例えば、米国特許第３
，８４７，８８１号明細書、米国特許第３，７６７゜６
３４壮明細書、西独特許公開第２，８１３，８９１号公
報、特公昭４９−３２７８８号公報などには、いくつか
のＣＴＦＥ／ＥＴ系共重合体が開示されている。[Prior Art] In recent years, flame-retardant resins that exhibit a high oxygen index, low smoke generation, and low drip properties have been attracting attention as coating materials for plenum electric wires, fire prevention materials, and the like. One of the resins with such characteristics is chlorotrifluoroethylene (hereinafter referred to as CTFE).
Fluorine-containing copolymers of ethylene (hereinafter abbreviated as ET) and ethylene (hereinafter abbreviated as ET) are known. For example, U.S. Pat.
, 847,881, U.S. Patent No. 3,767゜6
Some CTFE/ET-based copolymers are disclosed in the specification of No. 34 So, West German Patent Publication No. 2,813,891, Japanese Patent Publication No. 32788/1988, and the like.
しかしながら、従来知られているＣＴＦＥ／ＥＴ系共重
合体は、一般的にその熱分解点が３２０℃程度と低く、
また幾分高い熱分解点を有する含フッ素共重合体では、
その融点が２５０℃以上と高くなってしまい、いずれに
しても成形温度範囲が狭いという難点があった。而して
。However, conventionally known CTFE/ET copolymers generally have a low thermal decomposition point of about 320°C.
In addition, fluorine-containing copolymers with a somewhat high thermal decomposition point,
The melting point is as high as 250° C. or higher, and in any case, there is a problem that the molding temperature range is narrow. Then.
Ｌ記公知の明細書、公報などにおいては、テトラフルオ
ロエチレン（以下、ＴＦＥと略記する）とＥＴの共重合
体、ＣＴＦＥ／ＴＦＥ／ＥＴ系共重合体なども開示され
ているが、これらは酸素指数が小さいとか、あるいは燃
焼時に容易にドリップするなど、難燃性が必ずしも満足
できるものではなかった。In known specifications and publications, copolymers of tetrafluoroethylene (hereinafter abbreviated as TFE) and ET, CTFE/TFE/ET copolymers, etc. are also disclosed; Flame retardancy was not always satisfactory, such as a low index or easy dripping during combustion.
［発明の解決しようとする問題点］
本発明の目的は、前述のごとき従来技術における欠点を
解消しようとするものであり、高い熱分解点を有し、広
い成形温度範囲を持つ良成形性の難燃性樹脂を提供する
ことにある。[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned drawbacks in the prior art, and to provide a moldable material with good moldability that has a high thermal decomposition point and a wide molding temperature range. Our objective is to provide flame-retardant resin.
［問題点を解決するための手段］
本発明者は、前述の問題点を解決すべく、高い熱分解点
が期待できるが含フッ素共重合体について種々の研究、
検討を重ねた結果、次のごとき興味深い知見を得るに至
った。すなわち、ＣＴＦＥ 、ＴＦＥ 、及びＥＴの三
成分を組み合せて共重合することにより、高い熱分解点
を確保して良成形性の含フッ素共重合体が得られること
、また上記三成分の組成割合を特定範囲内にすることに
より、良成形性を保持して優れた難燃性が達成可能であ
るという新規知見を得たものである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventor has conducted various studies on fluorine-containing copolymers, which are expected to have a high thermal decomposition point.
As a result of repeated investigations, we came to the following interesting findings. That is, by copolymerizing a combination of the three components CTFE, TFE, and ET, a fluorine-containing copolymer with good moldability by ensuring a high thermal decomposition point can be obtained, and the composition ratio of the three components can be adjusted. This is a new finding that it is possible to maintain good moldability and achieve excellent flame retardancy by keeping the content within a specific range.
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、ＴＦＥ 、ＣＴＦＥ及びＥＴが共重合した含フ
ッ素共重合体からなり、その共重合体組成がＴ Ｆ Ｅ
１０〜６０モル％、ＣＴＦＥ２０〜６０モル％、ＥＴ
２０〜４０モル％であり、熱分解点が３２５℃以上であ
ることを特徴とする良成形性を有する難燃性樹脂を新規
に提供するものである。Thus, the present invention was completed based on the above findings, and consists of a fluorine-containing copolymer in which TFE, CTFE, and ET are copolymerized, and the copolymer composition is TFE.
10-60 mol%, CTFE 20-60 mol%, ET
The object of the present invention is to provide a new flame-retardant resin with good moldability, characterized by a thermal decomposition point of 20 to 40 mol % and a thermal decomposition point of 325° C. or higher.
本発明においては、ＴＦＥ 、ＣＴＦＥ及びＥＴの三成
分が特定の組成割合で共重合した含フッ素共重合体であ
ることが重要である。まず、ＥＴの割合は、余りに多量
すぎると酸素指数が小さくなり、優れた難燃性が達成さ
れず、また余りに少量すぎるとポリテトラフルオロエチ
レン、ポリグロロトリフルオロエチレンの如く溶融粘度
が高くなり、成形性が悪くなってしまうので、２０〜４
０モル％、特に２５〜３５モル％が好ましい。次に、Ｃ
ＴＦＨの割合は、余りに少量すぎると燃焼時容易にドリ
ップしてしまい、また余りに多量すぎると成形性が悪く
なるので、２０〜６０モル％、特に２０〜５５モル％が
好ましい、そして、ＴＦＥの割合は、余りに少量すぎる
場合には融点と熱分解点との差が小さくて成形性が悪く
なってしまい、また余りに多量すぎる場合には、溶融粘
度が高くて成形性が悪いので、１０〜６０モル％、特に
１５〜５５モル％が好ましい。In the present invention, it is important that the copolymer is a fluorine-containing copolymer in which the three components TFE, CTFE, and ET are copolymerized in a specific composition ratio. First, if the proportion of ET is too large, the oxygen index will be small and excellent flame retardancy will not be achieved, and if the proportion of ET is too small, the melt viscosity will be high, such as in polytetrafluoroethylene and polyglorotrifluoroethylene. 20 to 4 because the moldability will deteriorate.
0 mol%, especially 25 to 35 mol% is preferred. Next, C
The proportion of TFH is preferably 20 to 60 mol%, especially 20 to 55 mol%, because if it is too small, it will easily drip during combustion, and if it is too large, the moldability will be poor. If the amount is too small, the difference between the melting point and the thermal decomposition point will be small, resulting in poor moldability, and if it is too large, the melt viscosity will be high, resulting in poor moldability. %, especially 15 to 55 mol %.
上記本発明の特定含フッ素共重合体は、良好な成形性を
有し、且つ、優れた難燃性を示すものである。すなわち
、酸素指数が６０以上、例えば７６〜６０程度と高く、
燃焼時に炭化し、耐ドリップ性が良好である。また、融
点と分解点との差が１２０℃以上１例えば１４０〜１８
５℃程度と大きく、良好な成形性を有する。さらに１本
発明の特定含フッ素共重合体は、高い熱分解点を有し、
通常は３２５℃以上、好適な態様では３４０〜３７０℃
程度の熱分解点を達成可能である。なお、融点は上記熱
分解点と共に後述の分子量などによっても変り得るが、
通常は１７０〜２３０℃、特に１６０〜２２０℃程度が
好ましい。本発明において、特定含フッ素共重合体の分
子量は、電線用被覆材あるいは防火材として充分な機械
的強度を付与し、且つ良好な成形性を付与するために、
下記に定義する容量流速で５〜２０Ｑ＋ｓｍ３／秒程度
、特に１０〜１５０禦履３／秒が好ましい。The specific fluorine-containing copolymer of the present invention has good moldability and exhibits excellent flame retardancy. That is, the oxygen index is as high as 60 or more, for example around 76-60,
It carbonizes during combustion and has good drip resistance. In addition, the difference between the melting point and the decomposition point is 120°C or more 1, for example, 140 to 18
It has a large temperature of about 5°C and good moldability. Furthermore, the specific fluorine-containing copolymer of the present invention has a high thermal decomposition point,
Usually 325°C or higher, preferably 340-370°C
It is possible to achieve thermal decomposition points of about Note that the melting point may vary depending on the thermal decomposition point as well as the molecular weight described below.
Usually, the temperature is preferably about 170 to 230°C, particularly about 160 to 220°C. In the present invention, the molecular weight of the specific fluorine-containing copolymer is determined to provide sufficient mechanical strength as a coating material for electric wires or a fireproofing material, and to provide good moldability.
The capacity flow rate defined below is preferably about 5 to 20 Q+sm3/sec, particularly 10 to 150 Q+sm3/sec.
本明細書中にて使用される「容量流速」なるＨ Ｍは、
次の様に定義され、分子量の目安となるものである。す
なわち、高化式フローテスターを使用して、所定温度、
所定荷重３０ｋｇ／ｃ＋＊２のもとに、ノズル径１ｍｍ
、ランド２ｍｍのノズルよりＩｇの試料を押出し、その
際の単位時間に押出される溶融試料の容量で表わされる
値が、「容量流速」として定義され、その単位はｍｍ３
／秒である。ここにおいて、所定温度とは、特定の含フ
ッ素共重合体の成形可能な温度領域（融点と熱分解点と
の間の温度範囲）の内から採用される。而して、本発明
における特定の含フッ素共重合体に対しては、所定温度
として３００℃が選定される。As used herein, "volume flow rate" HM is:
It is defined as follows and serves as a guideline for molecular weight. In other words, using a Koka type flow tester, the specified temperature,
Nozzle diameter 1mm under specified load 30kg/c+*2
, the value expressed by the volume of the molten sample extruded per unit time when extruding an Ig sample from a nozzle with a land size of 2 mm is defined as the "volume flow rate", and its unit is mm3.
/second. Here, the predetermined temperature is selected from within the moldable temperature range (temperature range between the melting point and thermal decomposition point) of the specific fluorine-containing copolymer. Therefore, 300° C. is selected as the predetermined temperature for the specific fluorine-containing copolymer of the present invention.
本発明の含フッ素共重合体を製造するには、従来よりＴ
ＦＥやＣＴＦＥなどの共重合体について公知乃至周知の
重合方法が、特に限定されることなく採用可能であり１
例えば溶液重合、懸濁重合、乳化重合などいずれの方法
も使用できる。In order to produce the fluorine-containing copolymer of the present invention, conventionally T.
Any known or well-known polymerization method for copolymers such as FE and CTFE can be employed without particular limitation.
For example, any method such as solution polymerization, suspension polymerization, or emulsion polymerization can be used.
溶液重合において使用され得る重合開始剤としては、例
えばジー（クロロフルオロアシル）−パーオキサイド、
ジー（パーフルオロアシル）−パーオキサイド、ジー（
ω−ハイドロパーフルオロアシル）−パーオキサイド、
ｔ−ブチルパーオキシイソブチレート、ジイソプロピル
パーオキシジカーボネートなどが挙げられる。また、溶
媒としてはクロロフルオロアルカンが用いら、クロロフ
ルオロアルカンとしては、例えばトリクロロフルオロメ
タン、ジクロロジフルオロメタン、ジクロロフルオロメ
タン、クロロジフルオロメタン、トリフルオロメタン、
トリクロロトリフルオロエタン、ジクロロテトラフルオ
ロエタン、クロロペンタフルオロエタン、ジフルオロエ
タンなどが挙げられる。また必要に応じて分子量調整の
ための連鎖移動剤を添加しても良く１例えば四塩化炭素
、ｎ−ペンタン、ｎ−ヘキサン、インペンタン。Polymerization initiators that can be used in solution polymerization include, for example, di(chlorofluoroacyl)-peroxide,
G (perfluoroacyl) - peroxide, G (
ω-hydroperfluoroacyl)-peroxide,
Examples include t-butyl peroxyisobutyrate and diisopropyl peroxydicarbonate. In addition, a chlorofluoroalkane is used as a solvent, and examples of the chlorofluoroalkane include trichlorofluoromethane, dichlorodifluoromethane, dichlorofluoromethane, chlorodifluoromethane, trifluoromethane,
Examples include trichlorotrifluoroethane, dichlorotetrafluoroethane, chloropentafluoroethane, difluoroethane, and the like. Furthermore, a chain transfer agent may be added to adjust the molecular weight if necessary. Examples include carbon tetrachloride, n-pentane, n-hexane, and impentane.
トリクロロフルオロメタン、メタノールの如き連鎖移動
剤を使用するのが好ましい。Preferably, chain transfer agents such as trichlorofluoromethane and methanol are used.
懸濁重合においては、ラジカル重合開始剤として前記溶
液重合で挙げたと同様のものが使用でき、溶媒としては
水と前記溶液重合で挙げた如キクロロフルオロアルカン
との混合物が用いられ、混合比は通常重量比で水：クロ
ロフルオロアルカン＝１＝９〜９：ｌ、好ましくはｌ：
５〜５：ｌ程度である。また連鎖移動剤としては、前記
溶液重合のものを使用するのが望ましい、さらに、懸濁
安定剤として、フルオロカーボン系の乳化剤、例えばＣ
３ＦｕＣＯＯＮＨａ 、Ｃ３ＦｕＣＯＯＮＨａなどを添
加しても良い。In suspension polymerization, the same radical polymerization initiators as mentioned above for solution polymerization can be used, and the solvent used is a mixture of water and dichlorofluoroalkane as mentioned above for solution polymerization, and the mixing ratio is as follows. Normal weight ratio of water:chlorofluoroalkane=1=9 to 9:l, preferably l:
It is about 5-5:l. As the chain transfer agent, it is preferable to use the solution-polymerized one described above.Furthermore, as a suspension stabilizer, a fluorocarbon-based emulsifier, such as C
3FuCOONHa, C3FuCOONHa, etc. may be added.
乳化重合において使用され得るラジカル重合開始剤は、
通常の水溶性のラジカル重合開始剤が用いられる０例え
ば、ジサクシニックアシッドパーオキサイド、過硫酸ア
ンモニウム、過硫酸カリウム、ｔ−ブチルパーオキシイ
ソブチレート、 ２．２′−ジグアニル−２，２′−ア
ゾプロパンジハイドロクロライドなどである。溶媒とし
ては、水単独または水と有機溶媒の混合溶媒を用い得る
。有機溶媒としては、ｔ−ブタノール。Radical polymerization initiators that can be used in emulsion polymerization include:
Common water-soluble radical polymerization initiators are used, such as disuccinic acid peroxide, ammonium persulfate, potassium persulfate, t-butylperoxyisobutyrate, 2,2'-diguanyl-2,2'-azo Such as propane dihydrochloride. As the solvent, water alone or a mixed solvent of water and an organic solvent can be used. The organic solvent is t-butanol.
ジフルオロエタン、トリクロロトリフルオロエタンなど
が、また連鎖移動剤としては溶液重合で挙げたものが使
用され得る。乳化剤としては、フルオロカーボン系の乳
化剤が望ましく。Difluoroethane, trichlorotrifluoroethane, etc. can be used, and as the chain transfer agent, those mentioned for solution polymerization can be used. As the emulsifier, a fluorocarbon emulsifier is preferable.
例えばＣ３ＦｕＣＯＯＮＨａ 、Ｃ３ＦｕＣＯＯＮＨａ
などである。For example, C3FuCOONHa, C3FuCOONHa
etc.
北記の各種重合方法における重合条件も、特に限定され
ることなく、広範囲にわたって採用可イ侶であり、具体
的な重合方法１条件などは後述の実施例中にて例示され
る。The polymerization conditions in Kitaki's various polymerization methods are not particularly limited, and can be adopted over a wide range, and specific conditions for one polymerization method are exemplified in the examples below.
本発明の含フッ素共重合体は、広い成形温度範囲を持つ
ため、各種成形部品、パイプ、容器等の成形に広く利用
でき、特にその優れた難燃性により電線被覆材、電気部
品、建材部品、自動車・航空機部品等に好適に利用でき
、ｍｆｓやフィルム・シートへの利用も可能である。Since the fluorine-containing copolymer of the present invention has a wide molding temperature range, it can be widely used for molding various molded parts, pipes, containers, etc. In particular, its excellent flame retardancy allows it to be used in wire coating materials, electrical parts, and building material parts. It can be suitably used for automobile/aircraft parts, etc., and can also be used for mfs and films/sheets.
［実施例］
次に、実施例および比較例を示し、本発明をさらに具体
的に説明するが、かかる説明によって本発明が何ら限定
されるものでないことは勿論である。なお、融点、熱分
解点、共重合体組成、酸素指数、燃焼時のドリップ性の
測定は次の方法で行なった。[Examples] Next, the present invention will be explained in more detail by showing Examples and Comparative Examples, but it goes without saying that the present invention is not limited by such explanations. The melting point, thermal decomposition point, copolymer composition, oxygen index, and dripping property during combustion were measured by the following methods.
融点、熱分解点
島ｎｔ製作所製ＤＴ−３Ｄ型を用い、昇温速度ｌＯ℃／
分で室温から昇温し、融解曲線の最大値を融点とし、ま
た、熱重量曲線の減少し始めた点を熱分解点とした。Melting point, thermal decomposition point Using the DT-3D model manufactured by Shimant Seisakusho, the heating rate was 10℃/
The temperature was raised from room temperature in minutes, and the maximum value on the melting curve was taken as the melting point, and the point at which the thermogravimetric curve began to decrease was taken as the thermal decomposition point.
共重合体組成
共重合体の組成は、共重合体のフッ素含量及び塩素含量
より計算した。これらフッ素含量、塩素含量は、それぞ
れ以下の方法で測定した。Copolymer composition The composition of the copolymer was calculated from the fluorine content and chlorine content of the copolymer. The fluorine content and chlorine content were each measured by the following methods.
すなわち、フッ素含量は、共重合体の熱分解により発生
したフッ素を水溶液にトラップし、フッ化物イオン選択
性電極（米国コーニング社製Ｎｏ、４７６０４２）を用
いて測定した。また、塩素含量は、共重合体をシート状
に成形し、ケイ光Ｘ線分析装置（理学電気型ＩＫＦ ３
Ｇ６４％型）を用いて測定した。That is, the fluorine content was measured by trapping fluorine generated by thermal decomposition of the copolymer in an aqueous solution and using a fluoride ion selective electrode (No. 476042, manufactured by Corning, USA). The chlorine content was determined by molding the copolymer into a sheet and using a fluorescent X-ray analyzer (Rigaku Denki IKF 3).
G64% type).
覧皇皿Ｉ
ＪＩＳ Ｋ７２０１−１９７２の方法により、東洋精機
型キャンドル法燃焼試験機Ｎｏ、６０６を用いて行なっ
た。The test was conducted according to the method of JIS K7201-1972 using Toyo Seiki candle method combustion tester No. 606.
燃 、のドリップ
金網の上に厚さ０．５鵬層のシートのサンプルを乗せ、
斜め上方よりプロパンガスを用いたブンゼンバーナーに
よりサンプルを燃焼させ、燃焼後金網状に炭化物が残っ
たか残らなかったかでドリップ性の判定を行なった。A sheet sample with a thickness of 0.5 layers was placed on top of the drip wire mesh.
The sample was burned obliquely from above using a Bunsen burner using propane gas, and the drip property was determined based on whether or not carbide remained in the shape of a wire mesh after burning.
実施例１
排気され、攪拌された１２００ｍｆ２のステンレス鋼製
オートクレーブ中に６２８ｇのトリクロロトリフルオロ
エタン及び５８１ｇのトリクロロフルオロメタンを加え
、次いでクロロトリフルオロエチレ７［ｉ４．８ｇ、エ
チレン２．８ｇ、テトラフルオロエチレン１２０．８ｇ
をそれぞれ加えた。Ｗｌ拌下でオートクレーブの温度を
６５℃まで上げ、ｔ−ブチルパーオキシイソブチレート
をトリクロロトリフルオロエタンに４１．８ｇ／（２で
溶かした溶液５＋ＩＱを加えた。この時の圧力は、１２
ｋｇ／ｃｍ２であった０重合の開始に伴ないテトラフル
オロエチレン５０モル％、クロロトリフルオロエチレン
２０モル％、エチレン３０モル％の組成の混合ガスを圧
力が一定に保たれるように連続して追加した。Example 1 Into an evacuated and stirred 1200 mf2 stainless steel autoclave was added 628 g of trichlorotrifluoroethane and 581 g of trichlorofluoromethane, then 4.8 g of chlorotrifluoroethylene 7[i, 2.8 g of ethylene, 2.8 g of tetrafluoro 120.8g of ethylene
were added to each. The temperature of the autoclave was raised to 65°C under Wl stirring, and a solution of 41.8 g/(2) of t-butyl peroxyisobutyrate dissolved in trichlorotrifluoroethane (5+IQ) was added.The pressure at this time was 12
With the start of polymerization, a mixed gas having a composition of 50 mol% of tetrafluoroethylene, 20 mol% of chlorotrifluoroethylene, and 30 mol% of ethylene was continuously added so as to keep the pressure constant. Added.
重合を３時間行なった後、生成物を回収し、１５０℃で
９時間乾燥することによって、ポリマー５１ｇを得た。After 3 hours of polymerization, the product was collected and dried at 150° C. for 9 hours to obtain 51 g of polymer.
このポリマーの組成は、前記測定用により測定を行なっ
たところＴＦＥ／ＣＴＦ Ｅ ／ Ｅ Ｔ ＝ ４５／
２４／３１ （モル％）であった、さらに、融点、熱分
解点等の諸特性の測定を行ない、表１に示した。The composition of this polymer was measured using the above measurement method and was found to be TFE/CTFE/ET = 45/
Furthermore, various properties such as melting point and thermal decomposition point were measured and are shown in Table 1.
実施例２
最初に仕込んだ七ツマ−の重量を、クロロトリフルオロ
エチレン１０３．８ｇ、エチレン２．１ｇ 、テトラフ
ルオロエチレン８９．１ｇとし、追加した混合ガスの組
成を、テトラフルオロエチレン３５モル％、クロロトリ
フルオロエチレン３５モル％。Example 2 The weights of the initially charged 7-mer were 103.8 g of chlorotrifluoroethylene, 2.1 g of ethylene, and 89.1 g of tetrafluoroethylene, and the composition of the added mixed gas was 35 mol% of tetrafluoroethylene, 35 mol% chlorotrifluoroethylene.
エチレン３０モル％とした以外は実施例１と同様に実施
した０重合は３．５時間行ない、ポリマー３５ｇを得た
。このポリマーの組成は、ＴＦＥ／ＣＴ Ｆ Ｅ ／
Ｅ Ｔ ＝ ３３／３８／３１（モル％）であった、諸
特性を表１に示す。The zero polymerization was carried out in the same manner as in Example 1 except that the ethylene content was 30 mol %, and the polymerization was carried out for 3.5 hours to obtain 35 g of polymer. The composition of this polymer is TFE/CTFE/
E T =33/38/31 (mol%), various properties are shown in Table 1.
実施例３〜７
実施例１と同様の手順を用いて、初期仕込のモノマー組
成比及び追加仕込のモノマー組成比を下記の通りに選ぶ
ことにより、それぞれ組成の異なるポリマーを得た。Examples 3 to 7 Using the same procedure as in Example 1, polymers with different compositions were obtained by selecting the monomer composition ratio of the initial charge and the monomer composition ratio of the additional charge as shown below.
得られたポリマーの諸特性を表１に示す。Table 1 shows various properties of the obtained polymer.
比較例１〜３
実施例１と同様の手順を用いて初期仕込のモノマー組成
比及び追加仕込のモノマー組成比を変えることにより、
それぞれ組成の異なるポリマーすなわち比較例１ ：
ＴＦＥ／ＥＴ＝７０／３０（モル％）、比較例２ ：
ＴＦＥ／ＣＴＦＥ／ＥＴ＝２０／３１／４９ （モル
％）、比較例３ ： ＴＦＥ／ＣＴ Ｆ Ｅ／Ｅ Ｔ＝
９／４７／４５ （モル％）を得た。それぞれのポリマ
ーの特性を表１に示す。Comparative Examples 1 to 3 By using the same procedure as Example 1 and changing the monomer composition ratio of the initial charge and the monomer composition ratio of the additional charge,
Polymers with different compositions, namely Comparative Example 1:
TFE/ET=70/30 (mol%), Comparative Example 2:
TFE/CTFE/ET=20/31/49 (mol%), Comparative Example 3: TFE/CTFE/ET=
9/47/45 (mol %) was obtained. Table 1 shows the properties of each polymer.
［発明の効果］
本発明は、融点と熱分解点の差が１２０°Ｃ以りを有す
る良成形性、酸素指数が６０以上、燃焼時炭化してドリ
ップ性が改良された難燃性の如き優れた効果を有し、さ
らに本発明の含フッ素共玉合体は優れた電気的特性を有
しており、電線用被覆材として使用した場合には、難燃
性低発煙性゛心線として有用な効果が認められる。[Effects of the Invention] The present invention has good moldability with a difference between the melting point and the thermal decomposition point of 120°C or more, an oxygen index of 60 or more, and flame retardancy such as carbonization during combustion and improved drip properties. In addition to having excellent effects, the fluorine-containing conjugate of the present invention also has excellent electrical properties, and when used as a coating material for electric wires, it is useful as a flame-retardant and low-smoke core wire. A significant effect was observed.
Claims (1)
レン及びエチレンが共重合した含フッ素共重合体からな
り、その共重合体組成がテトラフルオロエチレン１０〜
６０モル％、クロロトリフルオロエチレン２０〜６０モ
ル％、エチレン２０〜４０モル％であり、熱分解点が３
２５℃以上であることを特徴とする良成形性を有する難
燃性樹脂。 ２、含フッ素共重合体の融点と熱分解点の差が１２０℃
以上である特許請求の範囲第１項記載の難燃性樹脂。 ３、含フッ素共重合体の酸素指数が６０以上である特許
請求の範囲第１項〜第２項のいずれかに記載の難燃性樹
脂。 ４、含フッ素共重合体が燃焼時に炭化し耐ドリップ性が
良好である特許請求の範囲第１項〜第３項のいずれかに
記載の難燃性樹脂。[Scope of Claims] 1. Consisting of a fluorine-containing copolymer obtained by copolymerizing tetrafluoroethylene, chlorotrifluoroethylene, and ethylene, the copolymer composition is 10 to 10% of tetrafluoroethylene.
60 mol%, chlorotrifluoroethylene 20-60 mol%, ethylene 20-40 mol%, and the thermal decomposition point is 3.
A flame-retardant resin having good moldability characterized by a temperature of 25°C or higher. 2. The difference between the melting point and thermal decomposition point of the fluorine-containing copolymer is 120℃
The flame-retardant resin according to claim 1, which is as follows. 3. The flame-retardant resin according to any one of claims 1 to 2, wherein the fluorine-containing copolymer has an oxygen index of 60 or more. 4. The flame-retardant resin according to any one of claims 1 to 3, wherein the fluorine-containing copolymer is carbonized during combustion and has good drip resistance.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE8686116733T DE3677912D1 (en) | 1985-12-18 | 1986-12-02 | FLAME RETARDANT RESIN. |
| EP86116733A EP0226116B1 (en) | 1985-12-18 | 1986-12-02 | Flame-retardant resin |
| US06/938,857 US4730029A (en) | 1985-12-18 | 1986-12-08 | Flame-retardant resin |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28277485 | 1985-12-18 | ||
| JP60-282774 | 1985-12-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62230803A true JPS62230803A (en) | 1987-10-09 |
| JP2539793B2 JP2539793B2 (en) | 1996-10-02 |
Family
ID=17656899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61149688A Expired - Fee Related JP2539793B2 (en) | 1985-12-18 | 1986-06-27 | Flame-retardant resin with good moldability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2539793B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013525556A (en) * | 2010-04-30 | 2013-06-20 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | VDF polymer composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4825415A (en) * | 1971-08-04 | 1973-04-03 | ||
| JPS4932786A (en) * | 1972-07-27 | 1974-03-26 | ||
| JPS5925739A (en) * | 1982-08-04 | 1984-02-09 | 呉羽化学工業株式会社 | Modification of mucous surface of mucous adjusting material |
| JPS5925806A (en) * | 1982-08-04 | 1984-02-09 | Mitsubishi Rayon Co Ltd | Preparation of novel polymer composition |
-
1986
- 1986-06-27 JP JP61149688A patent/JP2539793B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4825415A (en) * | 1971-08-04 | 1973-04-03 | ||
| JPS4932786A (en) * | 1972-07-27 | 1974-03-26 | ||
| JPS5925739A (en) * | 1982-08-04 | 1984-02-09 | 呉羽化学工業株式会社 | Modification of mucous surface of mucous adjusting material |
| JPS5925806A (en) * | 1982-08-04 | 1984-02-09 | Mitsubishi Rayon Co Ltd | Preparation of novel polymer composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013525556A (en) * | 2010-04-30 | 2013-06-20 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | VDF polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2539793B2 (en) | 1996-10-02 |
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