JPH04277527A - Production of silicone-modified polyolefin resin - Google Patents
Production of silicone-modified polyolefin resinInfo
- Publication number
- JPH04277527A JPH04277527A JP6260191A JP6260191A JPH04277527A JP H04277527 A JPH04277527 A JP H04277527A JP 6260191 A JP6260191 A JP 6260191A JP 6260191 A JP6260191 A JP 6260191A JP H04277527 A JPH04277527 A JP H04277527A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyolefin resin
- siloxane
- oxazoline
- silicone
- 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
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims abstract description 17
- -1 amino, carboxyl Chemical group 0.000 abstract description 22
- 239000004033 plastic Substances 0.000 abstract description 10
- 229920003023 plastic Polymers 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 229920000578 graft copolymer Polymers 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 229920000098 polyolefin Polymers 0.000 description 9
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 102220050189 rs376049280 Human genes 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ポリオレフィン系樹脂
等の種々のプラスチックに離型性、耐摩耗性、潤滑性等
を付与するための添加剤として好適に用いられるシリコ
ーン変性ポリオレフィン系樹脂の製造方法に関する。[Industrial Application Field] The present invention relates to the production of silicone-modified polyolefin resins that are suitably used as additives to impart mold release properties, wear resistance, lubricity, etc. to various plastics such as polyolefin resins. Regarding the method.
【０００２】0002
【従来の技術】従来から、ポリオレフィン系樹脂の成形
時の離型性を改善するため或いは耐磨耗性、潤滑性等の
界面特性を付与するために、ポリシロキサンをポリオレ
フィン系樹脂に直接ブレンドすることが行われている。
しかしながら、この方法でポリシロキサンをブレンドし
た場合、ポリオレフィン系樹脂の成形或いは混練を行う
際にポリシロキサンがブリードアウトするため、ポリオ
レフィン系樹脂中にポリシロキサンを均一に分散させる
ことができず、従ってポリシロキサン特有の界面特性を
ポリオレフィン系樹脂に均一に付与することができない
という問題点がある。[Prior Art] Conventionally, polysiloxane has been directly blended into polyolefin resins in order to improve the mold release properties during molding of polyolefin resins or to impart interfacial properties such as abrasion resistance and lubricity. things are being done. However, when polysiloxane is blended using this method, the polysiloxane bleeds out during molding or kneading of the polyolefin resin, making it impossible to uniformly disperse the polysiloxane in the polyolefin resin. There is a problem in that the interfacial properties unique to siloxane cannot be uniformly imparted to polyolefin resins.
【０００３】0003
【発明が解決しようとする課題】この問題点を解決した
方法として、ラジカル重合法或いはアニオン重合法によ
ってオレフィンとシロキサンとを重合することによりシ
リコーン変性ポリオレフィン樹脂を合成する試みがなさ
れているが、この方法は収率が低く、経済的ではない。[Problems to be Solved by the Invention] As a method for solving this problem, attempts have been made to synthesize silicone-modified polyolefin resins by polymerizing olefins and siloxanes using radical polymerization or anionic polymerization. The method has low yield and is not economical.
【０００４】これに代わる方法として、特開平２−１１
７９２２号公報及び特開昭６３−１０１４８２号公報で
は、極性官能基を有するポリオレフィンに反応性のポリ
シロキサンを反応させてグラフト化し、得られたグラフ
ト物をポリオレフィンに溶融混練する方法が提案されて
いるが、更にポリオレフィン系樹脂等のプラスチックに
ブレンドされて、ブリードアウトを生じることなく良好
な界面特性を与えるシリコーン変性樹脂が望まれる。ま
た、上記提案の方法において主として用いるポリシロキ
サンは官能性有機基を片末端に導入した片末端型ポリシ
ロキサンであり、両末端型ポリシロキサンが用いられな
いのは三次元化などの副反応が起こりやすいためである
が、両末端型反応性ポリシロキサンを用いても上記三次
元化などの副反応が起こらないような反応条件下でグラ
フト化したグラフト物を用いてシリコーン変性樹脂を製
造する方法の開発が要望されている。[0004] As an alternative method, Japanese Patent Laid-Open No. 2-11
No. 7922 and JP-A-63-101482 propose a method in which a polyolefin having a polar functional group is reacted with a reactive polysiloxane to form a graft, and the resulting graft material is melt-kneaded with a polyolefin. However, there is a need for silicone-modified resins that can be blended with plastics such as polyolefin resins and provide good interfacial properties without causing bleed-out. In addition, the polysiloxane mainly used in the above proposed method is a single-end type polysiloxane in which a functional organic group is introduced at one end, and the reason why a double-end type polysiloxane is not used is that side reactions such as three-dimensionalization may occur. This is because it is easy to use, but it is a method for producing silicone-modified resin using a graft material that is grafted under reaction conditions that do not cause side reactions such as the three-dimensionalization described above even when using a double-terminated reactive polysiloxane. Development is required.
【０００５】本発明は上記事情に鑑みなされたもので、
ブリードアウトを起こすことなくポリオレフィン系樹脂
等に均一にブレンドされて、均一な耐摩耗性、潤滑性等
の界面特性を与える変性ポリオレフィン系樹脂を簡単に
、しかも両末端型反応性ポリシロキサンを用いた場合で
も三次元化などの副反応を起こすことなく製造する方法
を提供することを目的とする。[0005] The present invention has been made in view of the above circumstances.
A modified polyolefin resin that can be uniformly blended with polyolefin resins without bleed-out and provides uniform interfacial properties such as wear resistance and lubricity can be easily created using a double-terminated reactive polysiloxane. The purpose of the present invention is to provide a method for manufacturing the product without causing side reactions such as three-dimensionalization even in the case of three-dimensionalization.
【０００６】[0006]
【課題を解決するための手段及び作用】本発明者は上記
目的を達成するため鋭意検討を行った結果、ポリオレフ
ィン系樹脂として、反応性の高いオキサゾリン基を有す
るポリオレフィン系樹脂を用い、これに極性官能基を有
するシロキサン、好ましくは下記一般式（１）で示され
るシロキサンを反応させることにより、上記ポリオレフ
ィン系樹脂のオキサゾリン基に対して上記シロキサンが
開環反応することによりグラフト物が得られ、このグラ
フト物はブリードアウトを起こすことなくポリオレフィ
ン系樹脂に均一にブレンドされて良好な表面特性を与え
ることを知見した。また、上記オキサゾリン基を有する
ポリオレフィン系樹脂と極性官能基を有するシロキサン
との反応は、ポリシロキサンをトルエン還流下という比
較的緩和な反応条件でポリオレフィンにグラフトさせる
ことができるので、ポリシロキサンが両末端型であって
も三次元化などの副反応が起こることなくポリシロキサ
ンを上記ポリオレフィンにグラフトさせることができる
ことを知見し、本発明をなすに至った。[Means and effects for solving the problem] As a result of intensive studies to achieve the above object, the present inventor used a polyolefin resin having a highly reactive oxazoline group as the polyolefin resin, and By reacting a siloxane having a functional group, preferably a siloxane represented by the following general formula (1), the siloxane undergoes a ring-opening reaction with the oxazoline group of the polyolefin resin to obtain a grafted product. It was found that the grafted material was uniformly blended into the polyolefin resin without causing bleed-out and provided good surface properties. In addition, in the reaction between the polyolefin resin having an oxazoline group and the siloxane having a polar functional group, the polysiloxane can be grafted onto the polyolefin under relatively mild reaction conditions such as refluxing toluene. The present inventors have discovered that polysiloxane can be grafted onto the above polyolefin without causing side reactions such as three-dimensionalization even if the polyolefin is a mold, and the present invention has been completed.
【０００７】[0007]
【化１】
（式中Ｒ１は炭素数１〜１８のアルキル基又は炭素数２
〜１８の脂肪族又は芳香族炭化水素基を示し、Ｒ２は極
性官能基、特にアミノ基、カルボキシル基或いは水酸基
のような活性水素を有する反応基、もしくは該極性官能
基を含む基又はＲ１と同じ基を示すが、Ｒ２の少なくと
も一つは上記極性官能基もしくは該極性官能基を含む基
である。また、ｎは０〜１０，０００の整数である。）
以下、本発明につき更に詳しく説明すると、本発明のシ
リコーン変性ポリオレフィン系樹脂の製造方法は、オキ
サゾリン基を含有するポリオレフィン系樹脂に極性官能
基を有するシロキサンを反応させるものである。[Formula R1 is an alkyl group having 1 to 18 carbon atoms or 2 carbon atoms]
~18 aliphatic or aromatic hydrocarbon groups, R2 is a polar functional group, especially a reactive group having active hydrogen such as an amino group, a carboxyl group, or a hydroxyl group, or a group containing the polar functional group, or the same as R1 At least one of R2 is the above polar functional group or a group containing the polar functional group. Further, n is an integer from 0 to 10,000. )
The present invention will be described in more detail below. The method for producing a silicone-modified polyolefin resin of the present invention involves reacting a polyolefin resin containing an oxazoline group with a siloxane having a polar functional group.
【０００８】ここで、オキサゾリン基を含有するポリオ
レフィン系樹脂の主骨格をなすポリオレフィンはいずれ
のものでもよく、特に限定されるものではないが、ポリ
スチレン、アクリロニトリル−スチレン共重合体等のス
チレン共重合体が好ましく用いられ、これらのスチレン
骨格を含むポリオレフィンにオキサゾリンを共重合させ
たものが好適である。このようなものとして、下記構造
式（２）で示すものが例示され、このオキサゾリン−ス
チレン共重合体は反応性も高く、本発明に有効に用いら
れる。[0008] Here, the polyolefin forming the main skeleton of the polyolefin resin containing an oxazoline group may be any type, and is not particularly limited, but includes polystyrene, styrene copolymers such as acrylonitrile-styrene copolymers, etc. are preferably used, and those obtained by copolymerizing oxazoline with polyolefins containing these styrene skeletons are suitable. An example of such a polymer is one represented by the following structural formula (2), and this oxazoline-styrene copolymer has high reactivity and can be effectively used in the present invention.
【０００９】[0009]
【化２】 （但し、ｍ，ｋは正の整数である。）[Case 2] (However, m and k are positive integers.)
【００１０】上記オキサゾリン基を有するポリオレフィ
ン系樹脂の分子量は１０４〜１０６、特に１００，００
０〜５００，０００であることが好ましい。分子量が１
０４未満では成型品の強度が乏しく、分子量が１０６を
超えるとシロキサンとの反応性の低下や溶解度の低下が
起こる場合がある。[0010] The molecular weight of the polyolefin resin having an oxazoline group is 104 to 106, particularly 100,00
It is preferably 0 to 500,000. molecular weight is 1
If the molecular weight is less than 0.04, the strength of the molded product will be poor, and if the molecular weight exceeds 106, there may be a decrease in reactivity with siloxane or a decrease in solubility.
【００１１】また、オキサゾリン基を有するポリオレフ
ィン系樹脂中のオキサゾリン含有量は１〜１０％（重量
％、以下同じ）、特に１〜５％とすることが好ましく、
通常オキサゾリン基の数は１００以下、特に２０〜１０
０が好ましい。オキサゾリン含有量が１％未満では、オ
キサゾリン基を含有するポリオレフィン系樹脂とシロキ
サンとをグラフト化した場合、このグラフト物がシロキ
サンを含有し得る限界量が小さくなり、このためこのグ
ラフト物をポリオレフィンに添加しても十分な潤滑性を
付与することができない場合が生じる。一方、オキサゾ
リン含有量が１０％を超えると未反応のオキサゾリン基
が熱劣化する場合があるので、上記グラフト物を添加す
ることにより得られるシリコーン変性ポリオレフィン樹
脂の外観が悪化してしまう場合がある。[0011] Further, the oxazoline content in the polyolefin resin having an oxazoline group is preferably 1 to 10% (weight %, the same hereinafter), particularly 1 to 5%,
Usually the number of oxazoline groups is less than 100, especially 20 to 10
0 is preferred. When the oxazoline content is less than 1%, when a polyolefin resin containing an oxazoline group is grafted with siloxane, the limit amount of siloxane that can be contained in this grafted material becomes small, and therefore this grafted material is added to the polyolefin. However, there may be cases where sufficient lubricity cannot be imparted. On the other hand, if the oxazoline content exceeds 10%, unreacted oxazoline groups may be thermally degraded, and the appearance of the silicone-modified polyolefin resin obtained by adding the graft material may deteriorate.
【００１２】一方、本発明に用いるシロキサンは、上記
ポリオレフィン系樹脂のオキサゾリン基と反応し得る極
性官能基を有するものであればいずれのものも使用し得
るが、特に下記一般式（１）で示されるものが好適であ
る。On the other hand, as the siloxane used in the present invention, any siloxane can be used as long as it has a polar functional group that can react with the oxazoline group of the polyolefin resin, but in particular, siloxanes represented by the following general formula (1) can be used. It is preferable that the
【００１３】[0013]
【化３】
ここで、Ｒ１は炭素数１〜１８、好ましくは１〜６のア
ルキル基又は炭素数２〜１８、好ましくは６〜１０の脂
肪族又は芳香族炭化水素基であるが、特にメチル基であ
ることが最も好ましい。また、Ｒ２は極性官能基もしく
は極性官能基を含む基又は上記Ｒ１と同様の基を示すが
、少なくとも一つは極性官能基もしくは極性官能基を含
む基である。この場合、極性官能基としては、アミノ基
、カルボキシル基或いは水酸基等の活性水素を有する反
応基が挙げられる。更に、ｎは０〜１０，０００の整数
であるが、特に２０〜１００が好ましい。embedded image Here, R1 is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, or an aliphatic or aromatic hydrocarbon group having 2 to 18 carbon atoms, preferably 6 to 10 carbon atoms, but especially methyl Most preferably, it is a group. Further, R2 represents a polar functional group, a group containing a polar functional group, or a group similar to the above R1, and at least one of them is a polar functional group or a group containing a polar functional group. In this case, the polar functional group includes a reactive group having active hydrogen such as an amino group, a carboxyl group, or a hydroxyl group. Further, n is an integer from 0 to 10,000, with 20 to 100 being particularly preferred.
【００１４】なお、このポリシロキサンの重量平均分子
量は１００，０００以下、特に１，０００〜１０，００
０であることが好ましい。[0014] The weight average molecular weight of this polysiloxane is 100,000 or less, particularly 1,000 to 10,000.
Preferably, it is 0.
【００１５】上記オキサゾリン基含有ポリオレフィン系
樹脂に対するシロキサンのグラフト化反応は、該ポリオ
レフィン系樹脂に対して５〜４０％、より好ましくは１
０〜３０％のシロキサンを加え、溶剤中で反応させるか
或いは溶融混練により行うことが好ましい。シロキサン
配合量が５％未満では、ポリオレフィン系樹脂等にブレ
ンドして所望の表面特性を付与する場合、グラフト物（
シリコーン変性ポリオレフィン系樹脂）の配合量が多量
になり、また、シロキサン量が４０％を超えると、溶剤
中におけるオキサゾリン基含有ポリオレフィン系樹脂の
溶解度が低下し、反応に長時間を要する場合がある。[0015] The grafting reaction of siloxane to the oxazoline group-containing polyolefin resin is carried out in an amount of 5 to 40%, more preferably 1% to the polyolefin resin.
It is preferable to add 0 to 30% of siloxane and react in a solvent or by melt-kneading. If the amount of siloxane blended is less than 5%, when blending with polyolefin resin etc. to impart desired surface properties, the graft material (
When the amount of the silicone-modified polyolefin resin (silicone-modified polyolefin resin) is large and the amount of siloxane exceeds 40%, the solubility of the oxazoline group-containing polyolefin resin in the solvent decreases, and the reaction may take a long time.
【００１６】なお、上記両成分を溶剤中で反応させる場
合、その反応温度は５０〜１２０℃、特に８０〜１００
℃とすることが好ましく、反応時間は３〜２０時間、特
に５〜１０時間とすることが好ましい。溶融混練の場合
の反応温度は１８０〜２５０℃、特に２００〜２３０℃
とすることが好ましく、反応時間は１０〜３０分間、特
に１０〜２０分間とすることが好ましく、通常は２２０
〜２３０℃下において１５分間溶融混練される。[0016] When both of the above components are reacted in a solvent, the reaction temperature is 50 to 120°C, particularly 80 to 100°C.
℃, and the reaction time is preferably 3 to 20 hours, particularly 5 to 10 hours. The reaction temperature in the case of melt kneading is 180 to 250°C, especially 200 to 230°C.
The reaction time is preferably 10 to 30 minutes, particularly 10 to 20 minutes, and usually 220 minutes.
The mixture is melt-kneaded at ~230°C for 15 minutes.
【００１７】上記溶剤としては、トルエン，キシレン等
のような不活性溶媒、ＴＨＦ，アセトン，メチルエチル
ケトン等のような極性溶媒が挙げられる。この中で特に
トルエン、ＴＨＦが好ましい。Examples of the solvent include inert solvents such as toluene and xylene, and polar solvents such as THF, acetone and methyl ethyl ketone. Among these, toluene and THF are particularly preferred.
【００１８】本発明のシリコーン変性ポリオレフィン系
樹脂は、ポリオレフィン系樹脂等のプラスチックにブレ
ンドし、その表面特性を改善するために使用することが
でき、この場合、上記プラスチックとしては、シリコー
ン変性ポリオレフィン系樹脂のポリオレフィンと同種又
は異種のものが好ましい。The silicone-modified polyolefin resin of the present invention can be blended with a plastic such as a polyolefin resin and used to improve the surface properties of the plastic. In this case, the plastic is a silicone-modified polyolefin resin. Polyolefins of the same type or different type are preferred.
【００１９】ブレンド方法は常法によって行うことがで
き、通常プラスチックに上記シリコーン変性ポリオレフ
ィン系樹脂を溶融混練することによって行われる。この
場合、シリコーン変性ポリオレフィン系樹脂の添加量は
、プラスチックに対しシロキサン含有量が０．５〜１０
％、特に１〜５％となるような量とすることが好ましい
。シロキサン含有量が０．５％未満ではシロキサン特有
の潤滑性等を十分に付与することができない場合があり
、また、１０％を超えるとシリコーン変性ポリオレフィ
ン系樹脂をブレンドしたプラスチックの機械的強度が低
下する場合がある。The blending method can be carried out by a conventional method, and is usually carried out by melt-kneading the above-mentioned silicone-modified polyolefin resin into a plastic. In this case, the amount of silicone-modified polyolefin resin added is such that the siloxane content is 0.5 to 10% of the plastic.
%, particularly preferably 1 to 5%. If the siloxane content is less than 0.5%, it may not be possible to sufficiently provide the lubricity characteristic of siloxane, and if it exceeds 10%, the mechanical strength of the plastic blended with silicone-modified polyolefin resin will decrease. There are cases where
【００２０】[0020]
【実施例】以下、実施例と比較例を示し、本発明を具体
的に説明するが、本発明は下記の実施例に制限されるも
のではない。[Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００２１】［実施例１］平均分子量（Ｍｗ）が１３万
でオキサゾリン含有量が１％のオキサゾリン−スチレン
共重合体４０ｇをトルエン３００ｇに溶解し、下記式（
３）で示される平均的片末端カルボン酸変性ポリシロキ
サン１０ｇを加え、９０℃で８時間加熱撹拌した。その
後トルエンを留去し、粉砕し、ポリシロキサン２０％含
有のグラフト物を得た。このグラフト物１６．７ｇとポ
リスチレン樹脂１５０ｇをシリンダー温度を２２０℃と
した押出し機で１５分間混練し、押し出した。[Example 1] 40 g of an oxazoline-styrene copolymer having an average molecular weight (Mw) of 130,000 and an oxazoline content of 1% was dissolved in 300 g of toluene, and the following formula (
10 g of the average one-end carboxylic acid-modified polysiloxane shown in 3) was added, and the mixture was heated and stirred at 90° C. for 8 hours. Thereafter, toluene was distilled off and the mixture was pulverized to obtain a grafted product containing 20% polysiloxane. 16.7 g of this graft material and 150 g of polystyrene resin were kneaded for 15 minutes in an extruder with a cylinder temperature of 220° C., and then extruded.
【００２２】[0022]
【化４】[C4]
【００２３】［実施例２］実施例１で用いたオキサゾリ
ン−スチレン共重合体の代わりにオキサゾリン含有量が
５％で平均分子量が１３万のオキサゾリン−スチレン共
重合体を用いた以外は実施例１と同様の操作を行った。
得られた成形物の物性を表１に示す。[Example 2] Example 1 except that an oxazoline-styrene copolymer having an oxazoline content of 5% and an average molecular weight of 130,000 was used instead of the oxazoline-styrene copolymer used in Example 1. The same operation was performed. Table 1 shows the physical properties of the molded product obtained.
【００２４】［実施例３］実施例１で用いたオキサゾリ
ン−スチレン共重合体の代わりにオキサゾリン含有量が
５％、平均分子量が２５万のアクリロニトリル−スチレ
ン共重合体を用いた以外は実施例１と同様の操作を行っ
た。得られた成形物の物性を表１に示す。[Example 3] Example 1 except that an acrylonitrile-styrene copolymer having an oxazoline content of 5% and an average molecular weight of 250,000 was used instead of the oxazoline-styrene copolymer used in Example 1. The same operation was performed. Table 1 shows the physical properties of the molded product obtained.
【００２５】［実施例４］オキサゾリン含有量が５％、
平均分子量が１３万のオキサゾリン−スチレン共重合体
４０ｇを用い、ポリシロキサンとして下記式（４）で示
す両末端カルボン酸変性ポリシロキサンを１７．１ｇ用
いて実施例１と同様に操作し、ポリシロキサン含有量が
３０％であるグラフト物を得た。このグラフト物１０．
７ｇをポリスチレン１５０ｇに添加し、実施例１と同様
にして組成物を得た。得られた成形物の物性を表１に示
す。[Example 4] Oxazoline content is 5%,
Using 40 g of an oxazoline-styrene copolymer with an average molecular weight of 130,000, and using 17.1 g of a polysiloxane modified with carboxylic acid at both ends represented by the following formula (4) as the polysiloxane, the same procedure as in Example 1 was carried out to obtain a polysiloxane. A graft material with a content of 30% was obtained. This graft 10.
A composition was obtained in the same manner as in Example 1 by adding 7 g to 150 g of polystyrene. Table 1 shows the physical properties of the molded product obtained.
【００２６】[0026]
【化５】[C5]
【００２７】上記実施例１〜４の組成物は、いずれもグ
ラフト物のブリードアウトがなく、グラフト物が均一に
ブレンドされていた。In all of the compositions of Examples 1 to 4, there was no bleed-out of the graft material, and the graft material was uniformly blended.
【００２８】［比較例１］実施例１と同じポリスチレン
樹脂を実施例１と同様にして押し出し成形した。得られ
た成形物の物性を表１に示す。[Comparative Example 1] The same polystyrene resin as in Example 1 was extruded in the same manner as in Example 1. Table 1 shows the physical properties of the molded product obtained.
【００２９】［比較例２］実施例１と同じポリスチレン
樹脂１５０ｇにジメチルポリシロキサン（粘度＝２９万
ｃｓ）３．１ｇを添加し、これを実施例１と同様にして
押出し機で混練し、押し出した。得られた成形物の物性
を表１に示す。この成形物は、樹脂表面にオイルが浮き
出し、ペインダブル性が低下したものであった。[Comparative Example 2] 3.1 g of dimethylpolysiloxane (viscosity = 290,000 cs) was added to 150 g of the same polystyrene resin as in Example 1, and this was kneaded in an extruder in the same manner as in Example 1, and extruded. Ta. Table 1 shows the physical properties of the molded product obtained. In this molded product, oil loomed out on the resin surface, resulting in poor paintability.
【００３０】[0030]
【表１】
＊１：引張試験はＪＩＳＫ７１１３に準拠して行った。
＊２：曲げ試験はＪＩＳＫ７２０３に準拠して行った。
＊３：動摩擦係数はＪＩＳＫ７２１８Ａに準拠し、相手
材 Ｓ５４Ｃ，速度１２ｃｍ／ｓ，荷重３．５ｋｇｆ
，保持時間５分の条件で測定した。[Table 1] *1: The tensile test was conducted in accordance with JISK7113. *2: The bending test was conducted in accordance with JISK7203. *3: Dynamic friction coefficient is based on JISK7218A, mating material S54C, speed 12cm/s, load 3.5kgf
, and a holding time of 5 minutes.
【００３１】[0031]
【発明の効果】本発明のシリコーン変性ポリオレフィン
系樹脂の製造方法は、プラスチックにブレンドされてブ
リードアウトが生じることなく表面特性を改善し得るシ
リコーン変性ポリオレフィン系樹脂を簡単にかつ穏和な
条件で定量的に得ることができ、両末端反応性ポリシロ
キサンを用いても三次元化などの不利な反応が起こらな
いという利点がある。Effects of the Invention The method for producing a silicone-modified polyolefin resin of the present invention can easily and quantitatively produce a silicone-modified polyolefin resin that can be blended with plastics and improve surface properties without causing bleed-out under mild conditions. It has the advantage that even if a polysiloxane with reactive terminals is used, disadvantageous reactions such as three-dimensionalization do not occur.
Claims (1)
ィン系樹脂に極性官能基を有するシロキサンを反応させ
ることを特徴とするシリコーン変性ポリオレフィン系樹
脂の製造方法。1. A method for producing a silicone-modified polyolefin resin, which comprises reacting a polyolefin resin containing an oxazoline group with a siloxane having a polar functional group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6260191A JP2630093B2 (en) | 1991-03-04 | 1991-03-04 | Method for producing silicone-modified polyolefin resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6260191A JP2630093B2 (en) | 1991-03-04 | 1991-03-04 | Method for producing silicone-modified polyolefin resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04277527A true JPH04277527A (en) | 1992-10-02 |
| JP2630093B2 JP2630093B2 (en) | 1997-07-16 |
Family
ID=13205016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6260191A Expired - Fee Related JP2630093B2 (en) | 1991-03-04 | 1991-03-04 | Method for producing silicone-modified polyolefin resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2630093B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7917268B2 (en) * | 2007-04-16 | 2011-03-29 | Honda Motor Co., Ltd | Vehicle clutch engagement control system and method |
-
1991
- 1991-03-04 JP JP6260191A patent/JP2630093B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7917268B2 (en) * | 2007-04-16 | 2011-03-29 | Honda Motor Co., Ltd | Vehicle clutch engagement control system and method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2630093B2 (en) | 1997-07-16 |
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