JPH034015B2 - - Google Patents
Info
- Publication number
- JPH034015B2 JPH034015B2 JP60017737A JP1773785A JPH034015B2 JP H034015 B2 JPH034015 B2 JP H034015B2 JP 60017737 A JP60017737 A JP 60017737A JP 1773785 A JP1773785 A JP 1773785A JP H034015 B2 JPH034015 B2 JP H034015B2
- Authority
- JP
- Japan
- Prior art keywords
- containing polyurethane
- molded
- poly
- diacetylene
- diacetylene group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004814 polyurethane Substances 0.000 claims description 28
- 229920002635 polyurethane Polymers 0.000 claims description 28
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims description 25
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000000465 moulding Methods 0.000 description 15
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000012669 compression test Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- JXMQYKBAZRDVTC-UHFFFAOYSA-N hexa-2,4-diyne-1,6-diol Chemical compound OCC#CC#CCO JXMQYKBAZRDVTC-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 poly(oxycarbonyliminohexamethyleneiminocarbonyloxy2,4-hexadiyne) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、歯車、カム等の精密機械部品として
有用な高剛性ジアセチレン基含有ポリウレタン成
形体の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a highly rigid diacetylene group-containing polyurethane molded body useful as precision mechanical parts such as gears and cams.
特定のジアセチレン化合物は、結晶状態で熱、
及びγ線または紫外線等の高エネルギー線によつ
て重合することはよく知られている(トポケミカ
ルポリメリゼーシヨン)。
Certain diacetylene compounds can be heated in their crystalline state,
It is well known that polymerization is caused by high-energy rays such as gamma rays or ultraviolet rays (topochemical polymerization).
しかし、ジアセチレン基を含有するポリウレタ
ンについては若干の報告あるもののその研究例は
少ない(Makromo.Chem.,134、219−229
(1970)、Arm.Khim.Zh.、23(11)、1004−1009
(1970)、USP3709860号等)。また、ジアセチレ
ン基含有ポリウレタンを成形し、高剛性の成形体
を得る試みは行なわれていない。 However, although there are some reports on polyurethanes containing diacetylene groups, there are few research examples (Makromo.Chem., 134 , 219-229
(1970), Arm.Khim.Zh., 23(11) , 1004−1009
(1970), USP No. 3709860, etc.). Further, no attempt has been made to obtain a highly rigid molded article by molding a diacetylene group-containing polyurethane.
本発明者らは、ジアセチレン構造の特性、特に
その高反応性に着目し、その高反応性を利用すべ
く鋭意研究の結果、ジアセチレン構造を含有する
ポリウレタンをその溶融温度以下の固相状態にお
いて高圧条件下で成形することによつて高剛性の
成形体を得ることに成効し、本発明に到達した。 The present inventors focused on the characteristics of the diacetylene structure, especially its high reactivity, and as a result of intensive research in order to take advantage of the high reactivity, the present inventors developed polyurethane containing a diacetylene structure in a solid state below its melting temperature. By molding under high pressure conditions, it was possible to obtain a highly rigid molded article, and the present invention was achieved.
すなわち、本発明は、ジアセチレン基含有ポリ
ウレタンを固相状態にて高圧条件下で成形するこ
とを特徴とする高剛性成形体の製造方法に関する
ものである。 That is, the present invention relates to a method for producing a highly rigid molded article, which is characterized by molding diacetylene group-containing polyurethane in a solid state under high pressure conditions.
本発明におけるジアセチレン基含有ポリウレタ
ンとは下記一般式(1)で表わされるユニツトを有す
る分子量が1×103〜1×105のポリマーである。 The diacetylene group-containing polyurethane in the present invention is a polymer having a unit represented by the following general formula (1) and having a molecular weight of 1×10 3 to 1×10 5 .
(式中、Rは炭素数2からの20のジイソシアナー
トのNCOを除いた残基である。)
本発明におけるジアセチレン基含有ポリウレタ
ンは常法に従い、有機ジイソシアナートとジアセ
チレン基含有ジオールである2,4−ヘキサジイ
ン−1,6−ジオールとの付加反応によつて合成
することができる。 (In the formula, R is a residue of a diisocyanate having 2 to 20 carbon atoms excluding NCO.) The diacetylene group-containing polyurethane in the present invention is prepared by combining an organic diisocyanate and a diacetylene group-containing diol in accordance with a conventional method. It can be synthesized by an addition reaction with 2,4-hexadiyne-1,6-diol.
有機ジイソシアナートとしては、ヘキサメチレ
ンジイソシアナート(HMDI)、イソホロンジイ
ソシアナート(IPDI)、4,4′−ジフエニルメタ
ンジイソシアナート(MDI)、2,4−トリレン
ジイソシアナート(2,4−TDI)、2,6−ト
リレンジイソシアナート(2,6−TDI)、メタ
キシリレンジイソシアナート(XDI)、1,5−
ナフタレンジイソシアナート、4,4′−シシクロ
ヘキシルメタンジイソシアナート(水添MDI)
等及びそれらの混合物を用いることができる。他
方、コモノマーである2,4−ヘキサジイン−
1,6−ジオールは常法によりプロパルギルアル
コールの酸化カツプリングにより合成できる。 Examples of organic diisocyanates include hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2, 4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), metaxylylene diisocyanate (XDI), 1,5-
Naphthalene diisocyanate, 4,4'-cyclohexylmethane diisocyanate (hydrogenated MDI)
etc. and mixtures thereof can be used. On the other hand, the comonomer 2,4-hexadiyne-
1,6-diol can be synthesized by oxidative coupling of propargyl alcohol in a conventional manner.
ジイソシアナート、ジオールの重付加反応によ
るポリウレタンの合成は、プラスチツク材料講座
〔2〕ポリウレタン樹脂(日刊工業新聞社)等の
成書に示されるポリウレタン製造の常法によつて
合成できる。 Polyurethane can be synthesized by the polyaddition reaction of diisocyanate and diol by a conventional method for producing polyurethane as described in books such as Plastic Materials Course [2] Polyurethane Resin (Nikkan Kogyo Shimbun).
ジアセチレン基含有ポリウレタンの分子量は特
に制限はないが、一般に1×103から1×105の間
である。また、ジアセチレン基含有ポリウレタン
の形状には制限がないが、好ましくは粉体状の形
状が用いられる。 The molecular weight of the diacetylene group-containing polyurethane is not particularly limited, but is generally between 1×10 3 and 1×10 5 . Further, although there is no limit to the shape of the diacetylene group-containing polyurethane, a powdery shape is preferably used.
本発明のジアセチレン基含有ポリウレタンの高
剛性成形体を製造する方法は、上記方法によつて
製造されたジアセチレン基含有ポリウレタンを固
体状態、高圧下で成形することに特徴がある。 The method for producing a highly rigid molded body of diacetylene group-containing polyurethane of the present invention is characterized in that the diacetylene group-containing polyurethane produced by the above method is molded in a solid state under high pressure.
高圧下で成形する方法としては、例えば、静水
圧加圧法などの加圧方法を使用できる。加圧圧力
は500気圧以上あれば良く、上限は特にない。好
ましくは1000気圧〜8000気圧である。又、加圧時
には大気圧下で加圧することによつて成形可能で
あるが、空隙のない成形体を得るためには加圧時
に加圧容器内や試料空隙の空気を排気し、減圧な
いし真空状態にして加圧成形することが好まし
い。 As a method for molding under high pressure, for example, a pressurization method such as a hydrostatic pressurization method can be used. The pressurizing pressure only needs to be 500 atmospheres or more, and there is no particular upper limit. Preferably it is 1000 atm to 8000 atm. Furthermore, when pressurizing, molding is possible by applying pressure under atmospheric pressure, but in order to obtain a molded product without voids, the air in the pressurized container and sample voids must be evacuated during pressurization, and the air must be reduced or vacuumed. It is preferable to form the product into a state and press-mold it.
加圧成形時の温度は、ジアセチレン基含有ポリ
ウレタンの溶融温度以下であればよく特に制限は
ない。好ましくは、室温(20℃)から200℃の範
囲であればよく、更に好ましくは50℃から150℃
の範囲である。この理由は、ジアセチレン基含有
ポリウレタンは約160℃から約200℃で発熱反応す
るためその温度以下で成形する必要があるためで
ある。 The temperature during pressure molding is not particularly limited as long as it is below the melting temperature of the diacetylene group-containing polyurethane. Preferably, the temperature range is from room temperature (20°C) to 200°C, more preferably from 50°C to 150°C.
is within the range of The reason for this is that diacetylene group-containing polyurethane undergoes an exothermic reaction at about 160°C to about 200°C, and therefore needs to be molded at a temperature below that temperature.
この様にして得られる本発明のジアセチレン基
含有ポリウレタン高剛性成形体は、その成形体の
圧縮弾性率が3GPa以上、特に6GPa以上に達して
いる極めて高剛性成形体であり、又、緻密性に優
れ硬度も高い成形体である。 The diacetylene group-containing polyurethane high-rigidity molded article of the present invention thus obtained is an extremely high-rigidity molded article having a compressive elastic modulus of 3 GPa or more, particularly 6 GPa or more, and has a high density and It is a molded product with excellent properties and high hardness.
本発明の実施により得られる成形体は上記の様
な優れた物性を持つており、切削や切断等の機械
加工が可能で任意の形状に加工できるので、歯
車、カム等の精密機械部品などの高度な物性を要
求される部品用材料として有用である。 The molded product obtained by implementing the present invention has excellent physical properties as described above, and can be machined into any shape by cutting or cutting, so it can be used for precision mechanical parts such as gears and cams. It is useful as a material for parts that require advanced physical properties.
また、このジアセチレン基含有ポリウレタンの
高圧下での成形時に、無機あるいは有機充てん
剤、顔料、紫外線吸収剤、安定剤等を配合して成
形することも可能である。 Furthermore, when this diacetylene group-containing polyurethane is molded under high pressure, it is also possible to add inorganic or organic fillers, pigments, ultraviolet absorbers, stabilizers, etc. to the molding process.
次に本発明を実施例にもつて更に具体的に示
す。文中、全て重量部をもつて示す。実施例は、
本発明の範囲を拘束するものではない。 Next, the present invention will be illustrated in more detail with reference to Examples. In the text, all parts are expressed in parts by weight. Examples are:
It is not intended to limit the scope of the invention.
参考例 1
ジアセチレン基含有ポリウレタンの製造
撹拌装置、滴下ロート、窒素導入管及び温度計
を装置した容量1の4口フラスコ内に、窒素気
流下2,4−ヘキサジイン−1,6−ジオール33
部(0.3モル)を乾燥N,N−ジメチルホルムア
ミド300部に溶解させ、更にウレタン化触媒とし
てジラウリン酸−ジ−n−ブチルスズ0.3部、ト
リエチルアミン0.5部加えた。Reference Example 1 Production of diacetylene group-containing polyurethane In a 4-necked flask with a capacity of 1 equipped with a stirring device, a dropping funnel, a nitrogen introduction tube, and a thermometer, 2,4-hexadiyne-1,6-diol 33 was added under a nitrogen stream.
(0.3 mol) was dissolved in 300 parts of dry N,N-dimethylformamide, and 0.3 part of di-n-butyltin dilaurate and 0.5 part of triethylamine were added as urethanation catalysts.
次いで、ヘキサメチレンジイソシアナート50.5
部(0.3モル)を撹拌下フラスコ内に適々加え、
1時間反応させた。続いて外部加熱により加熱し
60℃3時間反応させた。 Then hexamethylene diisocyanate 50.5
(0.3 mol) into the flask under stirring,
The reaction was allowed to proceed for 1 hour. Then, it is heated by external heating.
The reaction was carried out at 60°C for 3 hours.
反応終了後、反応液を3000部のメタノール中に
激しく撹拌しながら投入し、ジアセチレン基含有
ポリウレタンを再沈させた。 After the reaction was completed, the reaction solution was poured into 3000 parts of methanol with vigorous stirring to reprecipitate the diacetylene group-containing polyurethane.
得られた粉末状ポリウレタンを過し、更に
1000部のメタノールで洗浄し、減圧下約100時間
乾燥させた。 The obtained powdered polyurethane is filtered and further
It was washed with 1000 parts of methanol and dried under reduced pressure for about 100 hours.
生成物の収量は83部であつた。この生成物を
IRスペクトル、NMRスペクトルにより分析した
ところ、目的のポリ(オキシカルボニルイミノヘ
キサメチレンイミノカルボニルオキシ2,4−ヘ
キサジイン)(以下Poly(HMDI/2,4−HD)
と略す)であることが確認された。また、GPG
(ゲル・パーミエーシヨン・クロマトグラフ)に
よる分子量測定の結果、数平均分子量は3.6×104
(ポリスチレン換算)であつた。 The yield of product was 83 parts. this product
Analysis by IR spectrum and NMR spectrum revealed that the target poly(oxycarbonyliminohexamethyleneiminocarbonyloxy2,4-hexadiyne) (hereinafter referred to as Poly(HMDI/2,4-HD))
) was confirmed. Also, GPG
As a result of molecular weight measurement using (gel permeation chromatography), the number average molecular weight was 3.6×10 4
(polystyrene equivalent).
同様な方法にてジイソシアナートの種類を変更
し、イソホロンジイソシアナートよりのジアセチ
レン基含有ポリウレタンPoly(IPDI/2,4−
HD)、水添MDIよりPoly(水添MDI/2,4−
HD)MDIよりPoly(MDI/2,4HD)、TDIよ
りPoly(TDI/2,4−HD)、XDIよりPoly
(XDI/2,4−HD)を製造した。 Using the same method, the type of diisocyanate was changed, and diacetylene group-containing polyurethane Poly (IPDI/2,4-
HD), hydrogenated MDI to Poly(hydrogenated MDI/2,4-
HD) Poly from MDI (MDI/2,4HD), Poly from TDI (TDI/2,4-HD), Poly from XDI
(XDI/2,4-HD) was produced.
参考例 2
参考例1の2,4−ヘキサジイン−1,6−ジ
オールの代わりに、1,6−ヘキサンジオールを
用いて、アセチレン基を含有しないポリウレタン
〔ポリ(オキシカルボニルイミヘキサメチレンイ
ミノカルボニルオキシヘキサメチレン)(Poly
(HMDI/1,6−HDO))〕を製造した。Reference Example 2 In place of 2,4-hexadiyn-1,6-diol in Reference Example 1, 1,6-hexanediol was used to prepare a polyurethane containing no acetylene group [poly(oxycarbonylimihexamethyleneiminocarbonyloxyhexane)]. Methylene) (Poly
(HMDI/1,6-HDO)] was produced.
実施例 1
参考例1にて製造したジアセチレン基含有ポリ
ウレタン(Poly(HMDI/2,4−HD))0.7部
を、図1に示す成形器のシリンダー内につめ、内
部の空気を真空ポンプにより排気した。Example 1 0.7 parts of the diacetylene group-containing polyurethane (Poly(HMDI/2,4-HD)) produced in Reference Example 1 was packed into the cylinder of the molding machine shown in Figure 1, and the air inside was pumped out using a vacuum pump. Exhausted.
予じめ130℃に加熱しておいた油圧プレス上に
成形器を置き、そのまま5分間予熱した。続い
て、加圧圧力7960Kg/cm2、加圧時間10分加圧成形
した。得られた成形体は厚さ約2mm長径20mmの暗
赤色の円板状であつた。 The molding machine was placed on a hydraulic press that had been preheated to 130°C, and the molding machine was preheated for 5 minutes. Subsequently, pressure molding was carried out at a pressure of 7960 Kg/cm 2 for a time of 10 minutes. The obtained molded body was in the shape of a dark red disk with a thickness of about 2 mm and a major axis of 20 mm.
得られた成形体を高さ14mm、幅13mm、厚さ2mm
の直方体に切り出し、試験片とし、試験速度0.5
mm/分の条件下で、オートグラフDSS−500形
(島津製作所製)にて圧縮試験を行つた。この圧
縮弾性率は3.9GPa、圧縮強度は98MPaであつた。 The obtained molded body is 14 mm in height, 13 mm in width, and 2 mm in thickness.
Cut out a rectangular parallelepiped, use it as a test piece, and test at a test speed of 0.5
A compression test was conducted using an Autograph DSS-500 model (manufactured by Shimadzu Corporation) under conditions of mm/min. The compressive elastic modulus was 3.9 GPa and the compressive strength was 98 MPa.
比較例 1
参考例2にて製造したアセチレン基を含まない
ポリウレタン(Poly(HMDI/1,6−HDO)
を実施例1と同様な条件にて成形し、得られた成
形体の圧縮試験を行つた。得られた成形体の圧縮
弾性率は1.5GPa、強度は29MPaと非常に弱い成
形体であつた。Comparative Example 1 Polyurethane (Poly(HMDI/1,6-HDO) containing no acetylene group produced in Reference Example 2)
was molded under the same conditions as in Example 1, and the resulting molded product was subjected to a compression test. The obtained compact had a compressive modulus of elasticity of 1.5 GPa and a strength of 29 MPa, which was a very weak compact.
実施例 2
実施例1の成形条件を加圧時間10分から加圧時
間1時間と変化させ、同様な成形体を得、圧縮試
験を行つた。成形体の圧縮弾性率3.9GPa、圧縮
強度88MPaであつた。Example 2 A similar molded article was obtained by changing the molding conditions of Example 1 from 10 minutes to 1 hour, and a compression test was conducted. The compressive elastic modulus of the compact was 3.9 GPa and the compressive strength was 88 MPa.
実施例 3
実施例1の成形条件を加圧時間10分から加圧時
間4時間と変化させた。得られた成形体から高さ
13mm、幅10mm、厚さ1.8mmの試験片を切り出し圧
縮試験を行つた。得られた成形体の圧縮弾性率は
6.1GPa、圧縮強度は99MPaであつた。Example 3 The molding conditions of Example 1 were changed from 10 minutes to 4 hours. Height from the obtained molded body
A test piece of 13 mm, width 10 mm, and thickness 1.8 mm was cut out and subjected to a compression test. The compression modulus of the obtained compact is
The compressive strength was 6.1 GPa and 99 MPa.
実施例 4
実施例1のPoly(HMDI/2,4−HD)の代
わりにPoly(MDI/2,4−HD)を用い、加圧
圧力7960Kg/cm2加圧時間2時間で成形したとこ
ろ、同様な成形体が得られた。得られた成形体の
圧縮試験を行つたところ、圧縮弾性率4.8GPa、
圧縮強度120MPaであつた。Example 4 Poly (MDI/2,4-HD) was used instead of Poly (HMDI/2,4-HD) in Example 1 and molded at a pressure of 7960 Kg/cm 2 for 2 hours. A similar molded body was obtained. A compression test of the obtained molded body revealed that the compression modulus was 4.8GPa,
The compressive strength was 120 MPa.
実施例 5、6
実施例1のPoly(HMDI/2,4−HD)の代
わりにPoly(IPDI/2,4−HD)、Poly(水添
MDI/2,4−HD)を用い成形を行つたとこ
ろ、同様な成形体が得られた。Examples 5 and 6 Poly (IPDI/2,4-HD) and Poly (hydrogenated) were used instead of Poly (HMDI/2,4-HD) in Example 1.
When molding was performed using MDI/2,4-HD), a similar molded product was obtained.
実施例 7
実施例1のPoly(HMDI/2,4−HD)の成
形を押し込み金型で130℃で予熱5分、圧力4590
Kg/cm2で10分間加圧し、厚さ4mm、幅12.7mm、長
さ60mmの成形体を得た。この成形体を試験速度1
mm/分にて曲げ試験を行つたところ、曲げ弾性率
3.3GPa、曲げ強度0.99GPaであつた。Example 7 The Poly (HMDI/2,4-HD) of Example 1 was molded using a press mold, preheated at 130°C for 5 minutes, and the pressure was 4590°C.
Pressure was applied for 10 minutes at Kg/cm 2 to obtain a molded product having a thickness of 4 mm, a width of 12.7 mm, and a length of 60 mm. This molded body was tested at a test speed of 1
When a bending test was performed at mm/min, the bending elastic modulus was
It had a bending strength of 3.3 GPa and a bending strength of 0.99 GPa.
第1図は、成形装置の半分切欠断面図である。
図中、1は押棒、2は押え金具、3は外筒、4
は内筒、5は基盤、6は空気排出管、7は受け
棒、8はOリング押え、9は鐘面板、10はOリ
ング上、11はOリング下、12は成形樹脂粉末
である。
FIG. 1 is a half-cutaway sectional view of the molding device. In the figure, 1 is a push rod, 2 is a presser metal fitting, 3 is an outer cylinder, 4
1 is an inner cylinder, 5 is a base, 6 is an air discharge pipe, 7 is a receiving rod, 8 is an O-ring holder, 9 is a bell plate, 10 is above the O-ring, 11 is below the O-ring, and 12 is molded resin powder.
Claims (1)
子量が1×103〜1×105を有するジアセチレン基
含有ポリウレタンを高圧下にて成形することを特
徴とするジアセチレン基含有ポリウレタンの高剛
性成形体の製造方法。 (式中、Rは炭素数2から20のジイソシアナート
のNCOを除いた残基である。) 2 ジアセチレン基含有ポリウレタンの高剛性成
形体を製造するにあたつて、ジアセチレン基含有
ポリウレタンを固相状態で、500気圧以上の高圧
下室温以上200℃以下の条件下において成形する
ことを特徴のある特許請求の範囲第1項記載の高
剛性成形体の製造方法。[Scope of Claims] 1 A diacetylene group-containing polyurethane having a unit represented by the following general formula (1) and having a molecular weight of 1×10 3 to 1×10 5 is molded under high pressure. A method for producing a highly rigid molded article of acetylene group-containing polyurethane. (In the formula, R is the residue of a diisocyanate having 2 to 20 carbon atoms excluding NCO.) 2 In producing a highly rigid molded product of diacetylene group-containing polyurethane, diacetylene group-containing polyurethane 2. The method for producing a highly rigid molded article according to claim 1, wherein the product is molded in a solid state under high pressure of 500 atmospheres or more and at a temperature of room temperature or higher and 200° C. or lower.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60017737A JPS61177217A (en) | 1985-02-02 | 1985-02-02 | Manufacture of highly rigid molded body made of diacetylene group-containing polyurethane |
US06/818,744 US4654178A (en) | 1985-02-01 | 1986-01-14 | Process for production of highly rigid shaped product of polymer containing therein diacetylene group |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60017737A JPS61177217A (en) | 1985-02-02 | 1985-02-02 | Manufacture of highly rigid molded body made of diacetylene group-containing polyurethane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61177217A JPS61177217A (en) | 1986-08-08 |
JPH034015B2 true JPH034015B2 (en) | 1991-01-22 |
Family
ID=11952057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60017737A Granted JPS61177217A (en) | 1985-02-01 | 1985-02-02 | Manufacture of highly rigid molded body made of diacetylene group-containing polyurethane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61177217A (en) |
-
1985
- 1985-02-02 JP JP60017737A patent/JPS61177217A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS61177217A (en) | 1986-08-08 |
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