JPS638404A - Low-molecular weight ethylene copolymer - Google Patents
Low-molecular weight ethylene copolymerInfo
- Publication number
- JPS638404A JPS638404A JP15258086A JP15258086A JPS638404A JP S638404 A JPS638404 A JP S638404A JP 15258086 A JP15258086 A JP 15258086A JP 15258086 A JP15258086 A JP 15258086A JP S638404 A JPS638404 A JP S638404A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- meth
- copolymer
- maleic anhydride
- acrylic acid
- 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
- 229920001038 ethylene copolymer Polymers 0.000 title claims description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 229920001225 polyester resin Polymers 0.000 abstract description 8
- 239000004645 polyester resin Substances 0.000 abstract description 8
- 239000004952 Polyamide Substances 0.000 abstract description 7
- 239000002270 dispersing agent Substances 0.000 abstract description 5
- 239000000049 pigment Substances 0.000 abstract description 5
- 229920006122 polyamide resin Polymers 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- KPYCVQASEGGKEG-UHFFFAOYSA-N 3-hydroxyoxolane-2,5-dione Chemical group OC1CC(=O)OC1=O KPYCVQASEGGKEG-UHFFFAOYSA-N 0.000 abstract 1
- 239000003623 enhancer Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- -1 acrylic ester Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000012360 testing method 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〉 本発明はエチレン、（メタ）アクリル酸。[Detailed description of the invention] <Industrial application field> The present invention uses ethylene and (meth)acrylic acid.
無水マレイン酸を必須の構成単位とするポリアミド、ポ
リエステル樹脂等用の顔料分散剤。A pigment dispersant for polyamide, polyester resin, etc. that contains maleic anhydride as an essential constituent unit.
その他の用途に有用な低分子ｔｃエチレン系共重合体に
関するものである。The present invention relates to low molecular weight TC ethylene copolymers useful for other uses.
尚（メタ）アクリル酸エステルとはアクリル酸エステル
、メタアクリル酸エステル又はそれらの混合物を示し、
（メタ）アクリル酸とはアクリル酸、メタクリル酸又は
それらの混合物を意味する。In addition, (meth)acrylic ester refers to acrylic ester, methacrylic ester, or a mixture thereof,
(Meth)acrylic acid means acrylic acid, methacrylic acid or a mixture thereof.
〈従来の技術〉
従来からエチレン及びアクリル酸を構成単位とする低分
子量エチレン系共重合体は知られていた（例えば特公昭
５３−６５３８９号、特公昭５３−５７２９５号、特公
昭６０−７９００７号、特公昭６０−７９００８号）。<Prior art> Low molecular weight ethylene copolymers having ethylene and acrylic acid as constituent units have been known for a long time (for example, Japanese Patent Publication No. 53-65389, Japanese Patent Publication No. 53-57295, Japanese Patent Publication No. 60-79007). , Special Publication No. 60-79008).
この低分子量エチレン系共重合体はアンモニウム塩やア
ミン塩の形で分散液として紙用の接着剤に用いられたり
。This low molecular weight ethylene copolymer is used as a dispersion liquid in the form of ammonium salt or amine salt in paper adhesives.
あるいは共重合体そのままの形で樹脂用の顔料分散剤と
して用いられているが、極性樹脂例えば、ポリアミドや
ポリエステル樹脂に対しては相溶性が不充分であり物性
低下をきたす欠点が見られた。共重合体中のアクリル酸
単位の比率をかえたり、又共重合体の分子量をかえたり
して検討されたが、効果は必ずしも充分ではなかった。Alternatively, the copolymer itself is used as a pigment dispersant for resins, but it has the drawback of insufficient compatibility with polar resins such as polyamide and polyester resins, resulting in deterioration of physical properties. Attempts have been made to change the ratio of acrylic acid units in the copolymer or the molecular weight of the copolymer, but the effects were not necessarily sufficient.
〈発明が解決しようとする問題点〉 本発明の目的は、かかる問題点を解決し。<Problem that the invention seeks to solve> The purpose of the present invention is to solve such problems.
特をこポリアミド、ポリエステル樹脂等にすぐれた相溶
性を持つ低分子量エチレン系共重合体を提供することに
ある。In particular, it is an object of the present invention to provide a low molecular weight ethylene copolymer having excellent compatibility with polyamide, polyester resins, and the like.
〈問題点を解決するための手段〉
種々検討の結果、数平均分子量１７０００〜３３０００
のエチレン−（メタ）アクリル酸エステル−無水マレイ
ン酸共重合体を熱減成することにより得られる数平均分
子量が１０００〜１００００で分子中に（メタ）アクリ
ル酸単位及び無水マレイン酸単位を必須成分として含有
する低分子量エチレン共重合体が、この問題を解決する
ことを見いだした。<Means for solving the problem> As a result of various studies, the number average molecular weight was 17,000 to 33,000.
The number average molecular weight obtained by thermally degrading an ethylene-(meth)acrylic acid ester-maleic anhydride copolymer is 1000 to 10000, and the molecule contains (meth)acrylic acid units and maleic anhydride units as essential components. It has been found that a low molecular weight ethylene copolymer containing
無水マレイン酸単位の導入により、ナイロンやポリエス
テル樹脂との相溶性が向上する原因については必ずしも
明確ではないが、無水マレイン酸基がこれら樹脂中の極
性基となじみが特にすぐれているためと考えられる。The reason why the introduction of maleic anhydride units improves compatibility with nylon and polyester resins is not necessarily clear, but it is thought to be because maleic anhydride groups are particularly compatible with polar groups in these resins. .
該低分子量共重合体中の（メタ）アクリル酸単位は０．
３〜１０モル％、無水マレイン酸単位は０．２〜５モル
％であることが好ましい。The (meth)acrylic acid unit in the low molecular weight copolymer is 0.
It is preferable that the maleic anhydride unit is 3 to 10 mol %, and the maleic anhydride unit is 0.2 to 5 mol %.
（メタ）アクリル酸単位が上記範囲の含有量をはずれる
と樹脂との相溶性が低下する。If the content of (meth)acrylic acid units is outside the above range, the compatibility with the resin will decrease.
又無水マレイン酸含有量が０．２モル％以下では相溶性
向上効果が見られず、５モル％以上では強靭性が低下す
る。又低分子量エチレン共重合体の数平均分子量は１０
００〜１００００であることが好ましい。１０００以下
では樹脂との相溶性に劣りブリードアウトによる表面状
態不良の原因となり、又１００００以上では高純度のた
め加工作業性が劣る。該低分子量エチレン共重合体は各
構成単位のモノマーより重合舎こより製造することもで
きるが１分子量をＩ Ｑ００〜！ ００００にコントロ
ールするためには連鎖移動剤を多量に必要とし好ましく
な（・。Further, if the maleic anhydride content is 0.2 mol% or less, no effect of improving compatibility is observed, and if it is 5 mol% or more, the toughness decreases. Also, the number average molecular weight of the low molecular weight ethylene copolymer is 10
It is preferable that it is 00-10000. If it is less than 1,000, the compatibility with the resin will be poor, causing poor surface condition due to bleed-out, and if it is more than 10,000, the purity will be high, resulting in poor processing workability. The low molecular weight ethylene copolymer can also be produced from monomers of each structural unit in a polymerization factory, but the molecular weight is IQ00~! 0000 requires a large amount of chain transfer agent, which is not preferable.
これに対し、数平均分子量１７０００〜３３０００のエ
チレン、（メタ）アクリル酸エステル及び無水マレイン
酸共重合体を熱減成する方法は主鎖の切断による低分子
量化とエステルの酸への分解が同時におこり該低分子量
エチレン共重合体が容易に製造できる特徴がある。In contrast, the method of thermally degrading ethylene, (meth)acrylic acid ester, and maleic anhydride copolymers with number average molecular weights of 17,000 to 33,000 simultaneously lowers the molecular weight by cutting the main chain and decomposes the ester into an acid. This low molecular weight ethylene copolymer can be easily produced.
原料として用いる共重合体の数平均分子量が３３０００
以上では熱減成に多大のエネルギーを必要とし好ましく
なく、又１７０００以下のものでは共重合体のベレット
同志が融着する等作業性が低下し実際的ではない。The number average molecular weight of the copolymer used as a raw material is 33,000.
If the molecular weight is above 17,000, it requires a large amount of energy for thermal degradation, which is not preferable, and if it is below 17,000, the copolymer pellets may fuse together, resulting in poor workability, which is not practical.
なお、原料として使用するエチレン−（メタ）アクリル
酸エステル−無水マレイノ酸共重合体の数平均分子量は
、〔「高分子測定法。Note that the number average molecular weight of the ethylene-(meth)acrylic acid ester-maleino acid anhydride copolymer used as a raw material is determined by ["Polymer Measurement Method.
構造と物性（ト）」、高分子学会綿、培風館、昭和４８
年発行〕の第７６〜８９頁に記載されている方法を参考
として、ゲル浸透クロマトグラフィー法（ＧＰＣ）によ
って求められるものである。例えば、オルトジクロルベ
ンゼンを溶媒として、カラムオーブン温度１４５℃の条
件で測定した値を基に、単分散ポリスチレンを用いて作
成した平均分子鎖長とＧＰＣカウント数との検量線を使
つて数平均分子量として換算される。"Structure and Physical Properties (G)", Polymer Science Society of Japan, Baifukan, 1972
It is determined by gel permeation chromatography (GPC), with reference to the method described on pages 76 to 89 of ``Published in 2008''. For example, based on the values measured at a column oven temperature of 145°C using orthodichlorobenzene as a solvent, the number average is calculated using a calibration curve of average molecular chain length and GPC count number created using monodisperse polystyrene. Calculated as molecular weight.
一方２本発明による低分子量エチレン共重合体の数平均
分子量は、〔「高分子測定法、構造と物性（ト）、高分
子学会綿、培風館、昭和４８年発行〕の第５７〜７５頁
に記載されている方法を参考として、蒸気圧浸透圧法（
ＶＰＯ）によって求められるものである。例えば、ベン
ゼン溶媒を使用して、１．０重量％の溶液として、６０
℃で測定して求められる。On the other hand, the number average molecular weight of the low molecular weight ethylene copolymer according to the present invention can be found on pages 57 to 75 of "Polymer Measurement Method, Structure and Physical Properties (G), Polymer Science Society Watashi, Baifukan, published in 1972". Using the method described as a reference, vapor pressure osmotic pressure method (
VPO). For example, as a 1.0 wt% solution using benzene solvent, 60
Determined by measuring in °C.
（メタ）アクリル酸単位及び無水マレイン酸単位を０．
３〜１０モル％及び０．２〜５モル％含有する低分子量
エチレン共重合体は、（メタ）アクリル酸エステル単位
及び無水マレイン酸単以を各々０．３〜１２モル％及び
０．２〜５モル％含有する原料共重合体を用いて減成す
ることにより得られる。尚１条件によってはカルボン酸
の一部が分解することがあるため（メタ）アクリル酸エ
ステル単位の含有ｔの高めの原料重合体を用いることが
好ましい場合がある。(meth)acrylic acid units and maleic anhydride units are 0.
The low molecular weight ethylene copolymer containing 3 to 10 mol% and 0.2 to 5 mol% of (meth)acrylic acid ester units and maleic anhydride units of 0.3 to 12 mol% and 0.2 to 5 mol%, respectively. It is obtained by degradation using a raw material copolymer containing 5 mol%. Note that, depending on one condition, a part of the carboxylic acid may be decomposed, so it may be preferable to use a raw material polymer with a high content t of (meth)acrylic acid ester units.
（メタ）アクリル酸エステル単位のアルコール成分とし
ては０２以上の連鎖・分岐の脂肪族アルコール、例文ｌ
ｆエチルアルコール。The alcohol component of the (meth)acrylic acid ester unit is a chain/branched aliphatic alcohol of 02 or more, example sentence l
f ethyl alcohol.
イソプロピ／Ｌ／アルコール、ｎ−７’チルアルコール
等をあげることができる。より長鎖のアルコールを用い
ることもできるが、熱減成による低分子量化の工程でエ
ステルは分解して酸になるため長鎖のアルコールを用い
ることは実際的でない。又メチルエステルは減成により
酸になりに＜＜２本発明の原料として用いるのに好まし
くない。アルコール成分としては単品である必要はなく
、これらの混合物であってもよい。このエチレン、（メ
タ）アクリル酸エステル、無水マレイン酸共重合体は例
えば、フランス特許１３２３３７９号明細書記載の方法
で製造することができるが、上記要求をみたしておれば
その他の方法で得られる重合体でも使える。Examples include isopropyl/L/alcohol and n-7' methyl alcohol. Although longer chain alcohols can be used, it is impractical to use longer chain alcohols because the esters decompose into acids during the process of lowering the molecular weight by thermal degradation. In addition, methyl ester becomes an acid due to decomposition and is therefore not preferable for use as a raw material in the present invention. The alcohol component does not need to be a single item, and may be a mixture thereof. This copolymer of ethylene, (meth)acrylic acid ester, and maleic anhydride can be produced, for example, by the method described in French Patent No. 1,323,379, but it can also be produced by other methods as long as the above requirements are met. Can also be used with polymers.
本発明における熱減成とは、熱処理によって分子量を適
度に減少させることを（・う。Thermal degradation in the present invention refers to appropriately reducing the molecular weight by heat treatment.
熱誠或は３００〜５００℃、より好ましくは３５０〜４
５０℃で行われる。使用する原料及び所望される低分子
量共重合体の物性により熱減成の温度・時間は一定では
ない。酸素の存在は熱減成中着色及びゲル化をおこす原
因となるため不活性ガスの雰囲気下で行うのが好ましい
。熱減成の条件によっては未分解のエステルが残る場合
がある。低分子量エチレン共重合体が請求範囲の記載条
件をみたしているかぎり、残存するエステル含量につい
ては特に制限するものではないが２通常は（メタ）アク
リル酸及び（メタ）アクリル酸エステルの合計量中５０
モル％以上が（メタ）アクリル酸であることが好ましい
。Passionate or 300-500℃, more preferably 350-4
Performed at 50°C. The temperature and time of thermal degradation are not constant depending on the raw materials used and the desired physical properties of the low molecular weight copolymer. Since the presence of oxygen causes discoloration and gelation during thermal degradation, it is preferable to carry out the reaction under an inert gas atmosphere. Depending on the thermal degradation conditions, undecomposed esters may remain. As long as the low molecular weight ethylene copolymer satisfies the conditions stated in the claims, there is no particular restriction on the remaining ester content, but usually the total amount of (meth)acrylic acid and (meth)acrylic acid ester. middle school 50
It is preferable that at least mol% is (meth)acrylic acid.
共重合体のモノマーの含量は赤外線吸収スペクトルによ
り測定される。The monomer content of the copolymer is determined by infrared absorption spectroscopy.
得られた低分子量エチレン共重合体はポリアミド、ポリ
エステル樹脂等の顔料分散剤。The obtained low molecular weight ethylene copolymer is used as a pigment dispersant for polyamide, polyester resin, etc.
加工性改良剤、更には、アンモニウム塩、アミン塩とし
て水分散液として紙用の接着剤として有用である。以下
にポリアミド樹脂の顔料分散剤として用いた場合の効果
を示す。It is useful as a processability improver, and also as an adhesive for paper in the form of an aqueous dispersion as an ammonium salt or amine salt. The effects when used as a pigment dispersant for polyamide resin are shown below.
〈実施例〉
以下実施例により本発明を具体的に説明するが２本発明
はこれら実施例により何ら限定されろものではない。<Examples> The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例＝１
窒素導入管、温度計、排気ガス留出管及び攪拌捧をそな
えた３ｔ４つロコルベンに、エチレン−アクリル酸エチ
ルエステル−無水マレイン酸共重合体（数平均分子量３
１３００．アクリル酸エチルエステル単位の含有率１．
０モル％、無水マレイン酸単位の含有率０５モル％）ｔ
、５ＫＩＩを窒素雰囲気下で仕込む。以降熱減成終了ま
で、コルベン内に窒素は通気しつづける。次にマントル
ヒーターで加熱昇温し。Example = 1 A 3-ton four-piece Locolben equipped with a nitrogen inlet pipe, a thermometer, an exhaust gas distillation pipe, and a stirring rod was equipped with an ethylene-acrylic acid ethyl ester-maleic anhydride copolymer (number average molecular weight 3).
1300. Content of acrylic acid ethyl ester units 1.
0 mol%, content of maleic anhydride units 05 mol%)t
, 5KII under nitrogen atmosphere. From then on, nitrogen continues to be aerated into the Kolben until the thermal degradation is completed. Next, heat it up with a mantle heater.
攪拌しながら３６０℃で２時間熱減成を行った。Thermal degradation was performed at 360° C. for 2 hours while stirring.
次いで２００℃まで冷却後、熱減成物を取り出した。得
られた熱減成低分子量エチレン共重合体の数平均分子量
は４０００，７クリル酸単位の含有率は０．６モル％、
無水マレイン酸単位の含有率は０．４モル％であった。After cooling to 200° C., the heat-reduced product was taken out. The number average molecular weight of the obtained thermally degraded low molecular weight ethylene copolymer was 4000, the content of 7 acrylic acid units was 0.6 mol%,
The content of maleic anhydride units was 0.4 mol%.
実施例−２
エチレン−アクリル酸エチルエステル−無水マレイン酸
共重合体（数平均分子量２２８００゜アクＩＪ ）し酸
エチルエステル単位の含有率ｌＯモル％、無水マレイン
酸単位の含有率０．７モル％）を用い、実施例−１と同
様の操作で。Example-2 Ethylene-acrylic acid ethyl ester-maleic anhydride copolymer (number average molecular weight 22,800゜Ac IJ), content of acid ethyl ester units 10 mol%, content of maleic anhydride units 0.7 mol% ) in the same manner as in Example-1.
３９５℃で３０分間熱減成を行い、数平均分子量５ｏｏ
ｏ 、アクリル酸単位の含有率７．０モル％。Heat degradation was performed at 395°C for 30 minutes, and the number average molecular weight was 5oo.
o, content of acrylic acid units 7.0 mol%.
無水マレイン酸単位の含有率０．５モル％の低分子量エ
チレン共重合体を得た。A low molecular weight ethylene copolymer having a maleic anhydride unit content of 0.5 mol % was obtained.
比較例−１
エチレン−アクリル酸エチルエステル共重合体（数平均
分子量３２１００． アクリル酸エチルエステル単位含
有率４．７モル％）の共重合体を用い、実施例−１と同
様の操作で３６０℃。Comparative Example-1 A copolymer of ethylene-acrylic acid ethyl ester copolymer (number average molecular weight 32100, acrylic acid ethyl ester unit content 4.7 mol%) was used at 360°C in the same manner as in Example-1. .
２時間熱減成を行い、数平均分子量５０００ 。Heat degradation was performed for 2 hours, and the number average molecular weight was 5000.
アクリル酸単位の含有率３．０モル％の低分子量エチレ
ン共重合体を得た。A low molecular weight ethylene copolymer having an acrylic acid unit content of 3.0 mol% was obtained.
比較例−２
エチレン−アクリル酸エチルエステル共重合体（数平均
分子量３２７００ 、アクリル酸エチルエステル単位含
有率８．６モル％）の共重合体を用い、実施例−１と同
様の操作で３９０℃。Comparative Example-2 A copolymer of ethylene-acrylic acid ethyl ester copolymer (number average molecular weight 32,700, acrylic acid ethyl ester unit content 8.6 mol%) was used at 390°C in the same manner as in Example-1. .
３０分間熱減成を行い、数平均分子量８５００ 。Heat degradation was performed for 30 minutes, and the number average molecular weight was 8,500.
アクリル酸単位の含有率６．５モル％の低分子量エチレ
ン共重合体を得た。A low molecular weight ethylene copolymer having an acrylic acid unit content of 6.5 mol% was obtained.
比較例−３
数平均分子量３０８００ 、密度０．９１９のポリエチ
レンを用い、実施例−１と同様の操作で３５４’Ｃ，２
時間熱減成を行い、数平均分子量５０００の低分子量エ
チレン共重合体を得た。Comparative Example-3 Using polyethylene with a number average molecular weight of 30,800 and a density of 0.919, 354'C,2
Temporal thermal degradation was performed to obtain a low molecular weight ethylene copolymer with a number average molecular weight of 5,000.
上記の実施例および比較例に記述した熱減成法やこより
得られた各種の低分子量エチレン共重合体（５０重量部
）と銅フタロンアニンブルー顔料（５０重量部）とを表
面温度１２０℃に調節された３本ロールを使って１０分
間混練した後、冷却、粉砕して、 １０〜２０メツシ
ユのマスターパウダーを得た。Various low molecular weight ethylene copolymers (50 parts by weight) obtained by the thermal degradation method described in the above Examples and Comparative Examples and copper phthalonanine blue pigment (50 parts by weight) were mixed at a surface temperature of 120°C. The mixture was kneaded for 10 minutes using three rolls adjusted to the desired temperature, then cooled and pulverized to obtain a master powder of 10 to 20 meshes.
ポリアミド６（東し株式会社製、アミランＣＭ ｔｏｏ
ｌ ） １００重量部に該マスターパウダーを１重量部
配合し、 １０オンス射出成形機を用いて樹脂温度２４
５℃、金型温度７０℃の条件で各種の物性測定用の試験
片を作製した。射出成形性、成形物の表面状態、アイゾ
ツト衝撃強度と破断伸びの保持率（ペースポリアミドの
成形物と対比した値）を評価し、第１表に示す結果を得
た。Polyamide 6 (manufactured by Toshi Co., Ltd., Amilan CM too)
l) Add 1 part by weight of the master powder to 100 parts by weight, and use a 10-ounce injection molding machine to bring the resin temperature to 24.
Test pieces for measuring various physical properties were prepared under conditions of 5°C and mold temperature of 70°C. The injection moldability, surface condition of the molded product, retention of Izot impact strength and elongation at break (values compared to molded products of pace polyamide) were evaluated, and the results shown in Table 1 were obtained.
〈発明の効果〉
以上説明したように１本発明によれば、特）こポリアミ
ド、ポリエステル樹脂等にすぐれた相溶性を持つ低分子
量エチ、レン系共重合体を提供することができる。<Effects of the Invention> As explained above, according to the present invention, it is possible to provide a low molecular weight ethylene-based copolymer having excellent compatibility with polyamides, polyester resins, and the like.
Claims (3)
−（メタ）アクリル酸エステル−無水マレイン酸共重合
体を熱減成することにより得られる数平均分子量が１０
００〜１００００で分子中に（メタ）アクリル酸単位及
び無水マレイン酸単位とを必須成分として含有する低分
子量エチレン共重合体。(1) The number average molecular weight obtained by thermally degrading an ethylene-(meth)acrylic acid ester-maleic anhydride copolymer having a number average molecular weight of 17,000 to 33,000 is 10.
A low molecular weight ethylene copolymer having a molecular weight of 00 to 10,000 and containing (meth)acrylic acid units and maleic anhydride units as essential components in the molecule.
レイン酸共重合体中の（メタ）アクリル酸エステル単位
の含有率が０．３〜１２モル％、無水マレイン酸単位の
含有率が０．２〜５モル％である特許請求の範囲第１項
記載の低分子量エチレン共重合体。(2) The content of (meth)acrylic ester units in the ethylene-(meth)acrylic ester-maleic anhydride copolymer is 0.3 to 12 mol%, and the content of maleic anhydride units is 0.2 The low molecular weight ethylene copolymer according to claim 1, which has a content of 5 mol %.
酸単位の含有率が０．３〜１０モル％、無水マレイン酸
単位の含有率が０．２〜５モル％である特許請求の範囲
第１項もしくは第２項記載の低分子量エチレン共重合体
。(3) A claim in which the content of (meth)acrylic acid units in the low molecular weight ethylene copolymer is 0.3 to 10 mol%, and the content of maleic anhydride units is 0.2 to 5 mol%. The low molecular weight ethylene copolymer according to item 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15258086A JPH0672165B2 (en) | 1986-06-27 | 1986-06-27 | Low molecular weight ethylene random copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15258086A JPH0672165B2 (en) | 1986-06-27 | 1986-06-27 | Low molecular weight ethylene random copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS638404A true JPS638404A (en) | 1988-01-14 |
| JPH0672165B2 JPH0672165B2 (en) | 1994-09-14 |
Family
ID=15543571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15258086A Expired - Fee Related JPH0672165B2 (en) | 1986-06-27 | 1986-06-27 | Low molecular weight ethylene random copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0672165B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056076A (en) * | 2005-08-22 | 2007-03-08 | Japan Electric Cable Technology Center Inc | Manufacturing method of polyethylene-based modifier |
| JP2017513999A (en) * | 2014-04-28 | 2017-06-01 | ヴァレオ ビジョンＶａｌｅｏ Ｖｉｓｉｏｎ | Thermoplastic |
-
1986
- 1986-06-27 JP JP15258086A patent/JPH0672165B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056076A (en) * | 2005-08-22 | 2007-03-08 | Japan Electric Cable Technology Center Inc | Manufacturing method of polyethylene-based modifier |
| JP4593401B2 (en) * | 2005-08-22 | 2010-12-08 | 社団法人電線総合技術センター | Method for producing polyethylene-based modifier |
| JP2017513999A (en) * | 2014-04-28 | 2017-06-01 | ヴァレオ ビジョンＶａｌｅｏ Ｖｉｓｉｏｎ | Thermoplastic |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0672165B2 (en) | 1994-09-14 |
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