JPH03294327A - Production of urethane prepolymer containing terminal isocyanate group and having excellent storage stability - Google Patents
Production of urethane prepolymer containing terminal isocyanate group and having excellent storage stabilityInfo
- Publication number
- JPH03294327A JPH03294327A JP2098089A JP9808990A JPH03294327A JP H03294327 A JPH03294327 A JP H03294327A JP 2098089 A JP2098089 A JP 2098089A JP 9808990 A JP9808990 A JP 9808990A JP H03294327 A JPH03294327 A JP H03294327A
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- storage stability
- cpr
- prepolymer
- urethane prepolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 title claims description 4
- 229920005862 polyol Polymers 0.000 claims abstract description 37
- 150000003077 polyols Chemical class 0.000 claims abstract description 37
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- RJLZSKYNYLYCNY-UHFFFAOYSA-N ethyl carbamate;isocyanic acid Chemical group N=C=O.CCOC(N)=O RJLZSKYNYLYCNY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 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 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 101150055921 CPR5 gene Proteins 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 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 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 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 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
〔産業上の利用分野〕
本発明は、建築土木用防水材、床材、シーリング剤、注
型品、接着剤等のウレタン樹脂原料として用いられる、
貯蔵安定性の良好な末端イソシアネート基含有ウレタン
プレポリで−（以下ＮＣＯプレポリマーと略す）の製造
法に関するものである。
〔従来の技術〕
従来、ポリオールとポリイソシアネートとの灰地で、
ＮＧＯプレポリマーを製造する際、ポリオールのＣＰ
Ｒ（ＪＩＳ Ｋ １５７７−１９７０に基づく全塩基度
を意味する。以下同じ）を重要視して来た。その理由は
、ＣＰＨの原因となるアルカリ化合物が、ポリオールと
ポリイソシアネートの反応の触媒となる他、そのゲル化
を促進するためである（参考文献、岩田敬治著、日刊工
業新聞社発行、ポリウレタン樹脂、６５頁）、このアル
カリ化合物は、低分子アルコールまたは低分子アミンに
フルキレンオキシドを付加してポリオールを製造する際
に使用する苛性カリや苛性ソーダのようなアルカリ触媒
に基因するものである。そこでこのアルカリ触媒を除去
するため、酢酸、塩酸、硫酸のような酸性物質で中和後
、濾過助剤を添加して濾過して精製を行い、普通、ＣＰ
Ｒ１，０以下になるまで精製してからＮＣＯプレポリ
マーの原料に供してきた。
〔発明が解決しようとする課題〕
このように、貯蔵安定性の良好なＮＣＯプレポリマーを
得るためには、ＣＰＨの低い、例えばＣＰ １１．０以
下のポリオールを使用する必要があるが、このためには
、上記のように精製に充分配慮する必要があることから
、濾過に時間が長くかかり、これが自ずとコストアップ
の要因となる。
特に高分子量ポリオールを製造する場合は、製品の粘度
が高いため、加温して低粘度化しても濾過に長い時間が
かかり、精製費が高くなる。
従って、ＣＰＲ５０以下といった安価な粗製ポリオール
を原料として貯蔵安定性良好なＮＧＯプレポリマーを製
造することが工業的に要望されていた。
〔発明が解決しようとする課題〕
そこで本発明は１以上の要望に応え、ＣＰＲ５０以下と
いった安価な粗製ポリオールを原料として貯蔵安定性良
好なＮＣＯプレポリマーの製造方法を開発することを目
的とする。[Industrial Application Field] The present invention is used as a urethane resin raw material for waterproofing materials for construction and civil engineering, flooring materials, sealants, cast products, adhesives, etc.
The present invention relates to a method for producing a urethane prepolymer containing terminal isocyanate groups (hereinafter abbreviated as NCO prepolymer) having good storage stability. [Conventional technology] Conventionally, an ash base of polyol and polyisocyanate,
When producing NGO prepolymers, the CP of the polyol
Emphasis has been placed on R (meaning total basicity based on JIS K 1577-1970; the same shall apply hereinafter). The reason for this is that the alkali compound that causes CPH not only catalyzes the reaction between polyol and polyisocyanate, but also promotes their gelation (References, Keiji Iwata, published by Nikkan Kogyo Shimbun, polyurethane resin , p. 65), this alkaline compound is derived from an alkaline catalyst such as caustic potash or caustic soda used when producing a polyol by adding fullylene oxide to a low-molecular alcohol or low-molecular amine. Therefore, in order to remove this alkali catalyst, purification is performed by neutralizing with an acidic substance such as acetic acid, hydrochloric acid, or sulfuric acid, followed by filtration with the addition of a filter aid.
It has been purified to R1.0 or less and then used as a raw material for NCO prepolymer. [Problems to be Solved by the Invention] As described above, in order to obtain an NCO prepolymer with good storage stability, it is necessary to use a polyol with a low CPH, for example, a CP of 11.0 or less. Since it is necessary to pay sufficient attention to purification as described above, filtration takes a long time, which naturally causes an increase in costs. In particular, when producing high molecular weight polyols, the viscosity of the product is high, so even if the viscosity is lowered by heating, filtration takes a long time and refining costs increase. Therefore, there has been an industrial demand for producing an NGO prepolymer with good storage stability using an inexpensive crude polyol having a CPR of 50 or less as a raw material. [Problems to be Solved by the Invention] Therefore, the present invention aims to meet one or more demands and develop a method for producing an NCO prepolymer with good storage stability using an inexpensive crude polyol with a CPR of 50 or less as a raw material.
帽１を解決するための手段及び作用〕
（１）概要
以上の課題を解決するため、本発明は、ＣＰ１５０以下
のポリオールと、有機ポリイソシアネート化合物を、Ｉ
Ｉｃ：０１０Ｈ当量比１．３〜１０Ｇで反応させて末端
イソシアネートウレタンプレポリマーを製造するにあた
り、前記ポリオール中のＣＰＲを中和するに充分な酸性
化合物を添加することを特徴とする貯蔵安定性の良好な
末端イソシアネート基含有ウレタンプレポリマーの製造
法を要旨とする。
以下、発明の構成に関連する諸事項につき積別して説明
する。
（２）ポリオール
本発明で使用するポリオールとしては、例えばエチレン
グリコール、ジエチレングリコール、プロピレングリコ
ール、ジプロピレングリコール、ブチレンゲリコール、
テトラメチレングリコール、シフチレングリコール、ヘ
キシレングリコール、グリセリン、トリメチロールプロ
パン、ペンタエリスリトール、ビスフェノールＡ等の低
分子ポリオールに、アルキレンオキシド、例えばエチレ
ンオキシド、プロピレンオキシド、ブチレンオキシド等
を単独または混合付加重合して得られるポリエーテルポ
リオール等；及び前記ポリエーテルポリオール中でビニ
ルモノマー、例えばアクリルニトリル及び／又はスチレ
ンを重合させて得られる重合体ポリオール等が例示され
る。
そして、これらのポリオールは下記式で求められるＣＰ
Ｒが５０以下であることが必要である。
ＣＰＲ＝１０ｘ （Ａ−Ｂ）ｘｆ
ポリオールのＣＰＲが５０を超えた場合、ＮＣＯプレポ
リマーが着色したり、白濁の原因となったりして貯蔵安
定性が悪くなる。
（３）有機ポリイソシアネート化合物
本発明で使用する有機ポリイソシアネート化合物として
は１例えばトリレンジイソシアネート（ＴＤＩ）、ジフ
ェニルメタンジイソシアネート（ＭＤＩ）、粗ジフェニ
ルメタンジイソシアネート、液状ジフェニルメタンジイ
ソシアネート、ナフタレンジイソシアネート、キシリレ
ンジイソシアネー）（ＸＤＩ）、ヘキサメチレンジイソ
シアネート（ＭＤＩ）、 インフォロンジイソシアネ
ート（ＩＰＤＩ）、水素添加ＭＤＩ、水素添加ＸＤ１．
ＨＤＩのビュウレット化物、ＨＤＩのインシアヌレート
化物、ＩＰＤＩのインシアヌレート化物等が例示される
。
（４）酸性化合物
本発明において、ポリオールの中和に使用する酸性化合
物としては、リン酸、アクリル酸、硫酸、塩酸、ホウ酸
、リンゴ酸、シュウ酸、アジピン酸、フタル酸等の有機
及び／又は無機酸が挙げられる。酸性化合物の使用量は
前記式から求められるポリオールのＣＰＲ（１ＣＰＲは
ＫＯＨの１．８７ｐｐ腸に相当する）に基づ＜ ＫＯＨ
を中和するに充分な量であり、望ましくは存在するＫＯ
Ｈ量の０．８当量〜５倍当量である。
（５）反応比等
ポリオールと有機ポリイソシアネート化合物を反応させ
る場合、ＮＣ：０１０Ｈ当量比は１．３〜＋００である
のが好ましい、該比が１．３以下では、精製ＮＧＯプレ
ポリマーが不安定であり、１００以上では有機ポリイソ
シアネートモノマーが過剰となり実用性に欠ける。
酸性化合物は、予め粗製ポリオールに添加しても又は粗
製ポリオールと有機ポ、リイソシアネートとを反応させ
る際、同時に添加しても良い。
〔実施例〕
以下実施例及び比較例により発明実施の態様及び効果に
つき記述するが１例示は説明用のもので発明思想の限定
を考慮したものではない。
（１）ポリオールの製造例
耐圧オートクレーブ中にグリセリン５８部、苛性カリ１
５部を仕込み、１２０℃に加温しつつプロピレンオキシ
ド１０００部、エチレンオキシド３５００部を導入して
付加重合反応を行なった。
上の反応生成物に、合成硅酸アルミニウム４０部を加え
て５０℃で中和した後、１２０℃に加熱して減圧脱水し
てから、濾過助剤（合成硅酸マグネシウム）５部を加え
て吸引濾過した。
得られたポリオールは水酸基価２３．０部ｇＫＯＨ／ｇ
、ＣＰＲ５，Ｏであった。
実施例１
上記製造例で得たポリオール（ＣＰＲ５，Ｏ，水酸基価
２３．Ｏ腸ｇＫＯＨ／ｇ ） ８８３０部、トリＬ／７
ジイソシアネー） １３７０部、リン酸０．１４部（酸
のアルカリに対する当量比３．０）を１００ ’Ｃ！で
２時間反応させてＦ−Ｎ１１１：０５．０％、粘度１８
．０００ｃｐｓ／２０ ”Ｃ（７）プレポリマーを合成
した（Ｎ（：０１０Ｈ当量比４．１）。
得られたプレポリマーをＮ２シールして缶に貯蔵し、−
５℃、５時間、次いで３５℃、５時間のサイクルテスト
を６ケ月間繰り返し、開缶してＮＧＯプレポリマーの粘
度を測定したところ。
１８．５００ｃｐｓ／２０℃であり、ゲル化もなく安定
であった。
実施例２及び３
ポリオールの製造例に従ってＣＰＲ９，７と１４，３の
ポリオールを調製し１次に表−１に示す量のアクリル酸
及び硫酸をそれぞれ使用し、実施例１に従ってＮＧＯプ
レポリマーを合成し、同様のサイクルテストを実施した
ところ、６ケ月経過しても安定であった・
比較例１
実施例１のポリオール８６３部、トリレン／イソシアネ
ー） １３７部を１００℃で２時間反応させてＦ−ＮＣ
：０５．０％、粘度２０，０００ａ−、／２０℃のプレ
ポリマーを調製した。これを実施例１と同様にしてサイ
クルテストを実施したところゲル化していた。
以下、各実施例及び比較例の各ポリオールのＣＰＲ値、
プレポリマーの合成に使用した酸の種類と量及び得られ
たプレポリマーの貯蔵安定性を括して表示する。
表−１Means and Effects for Solving Problem 1] (1) Overview In order to solve the above problems, the present invention provides a polyol with a CP of 150 or less and an organic polyisocyanate compound,
A storage-stable method characterized by adding an acidic compound sufficient to neutralize CPR in the polyol when reacting at an Ic:010H equivalent ratio of 1.3 to 10G to produce a terminal isocyanate urethane prepolymer. The summary is a method for producing a good urethane prepolymer containing terminal isocyanate groups. Below, various matters related to the structure of the invention will be explained separately. (2) Polyol Examples of the polyol used in the present invention include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene gelcol,
Alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, etc., are added singly or in combination to low-molecular polyols such as tetramethylene glycol, cyphthylene glycol, hexylene glycol, glycerin, trimethylolpropane, pentaerythritol, and bisphenol A. Examples include the resulting polyether polyol; and a polymer polyol obtained by polymerizing a vinyl monomer, such as acrylonitrile and/or styrene, in the polyether polyol. And, these polyols have CP calculated by the following formula.
It is necessary that R is 50 or less. CPR=10x (A-B)xf If the CPR of the polyol exceeds 50, the NCO prepolymer may be colored or become cloudy, resulting in poor storage stability. (3) Organic polyisocyanate compounds Examples of the organic polyisocyanate compounds used in the present invention include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), crude diphenylmethane diisocyanate, liquid diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate) ( XDI), hexamethylene diisocyanate (MDI), infron diisocyanate (IPDI), hydrogenated MDI, hydrogenated XD1.
Examples include biuret-formed HDI, incyanurate-formed HDI, and in-cyanurate-formed IPDI. (4) Acidic compounds In the present invention, the acidic compounds used to neutralize the polyol include organic and/or Or an inorganic acid can be mentioned. The amount of acidic compound used is based on the CPR of the polyol determined from the above formula (1 CPR corresponds to 1.87 pp of KOH).
The amount of KO present is preferably sufficient to neutralize the
The amount is 0.8 to 5 times the amount of H. (5) Reaction ratio When reacting a polyol with an organic polyisocyanate compound, the NC:010H equivalent ratio is preferably 1.3 to +00. If the ratio is 1.3 or less, the purified NGO prepolymer will be unstable. If it is 100 or more, the organic polyisocyanate monomer becomes excessive and lacks practicality. The acidic compound may be added to the crude polyol in advance, or may be added at the same time when the crude polyol and the organic polyisocyanate are reacted. [Example] The embodiments and effects of the invention will be described below using Examples and Comparative Examples, but the examples are for illustrative purposes only and do not take into account any limitations on the idea of the invention. (1) Production example of polyol 58 parts of glycerin, 1 part of caustic potassium in a pressure-resistant autoclave
5 parts were charged, and while heating to 120°C, 1000 parts of propylene oxide and 3500 parts of ethylene oxide were introduced to carry out an addition polymerization reaction. After adding 40 parts of synthetic aluminum silicate to the above reaction product and neutralizing it at 50°C, it was heated to 120°C and dehydrated under reduced pressure, and then 5 parts of a filter aid (synthetic magnesium silicate) was added. Filtered with suction. The obtained polyol had a hydroxyl value of 23.0 parts gKOH/g
, CPR5,O. Example 1 Polyol obtained in the above production example (CPR5, O, hydroxyl value 23.0 gKOH/g) 8830 parts, tri L/7
diisocyanate) and 0.14 part of phosphoric acid (equivalence ratio of acid to alkali: 3.0) at 100'C! F-N111:05.0%, viscosity 18
．． 000 cps/20'' C(7) prepolymer was synthesized (N(:010H equivalent ratio 4.1). The obtained prepolymer was sealed with N2 and stored in a can.
A cycle test of 5 hours at 5°C and then 5 hours at 35°C was repeated for 6 months, the can was opened, and the viscosity of the NGO prepolymer was measured. The temperature was 18.500 cps/20°C, and it was stable without gelation. Examples 2 and 3 Polyols with CPR 9,7 and 14,3 were prepared according to polyol production examples, and then NGO prepolymers were synthesized according to Example 1 using acrylic acid and sulfuric acid in the amounts shown in Table 1, respectively. However, when a similar cycle test was conducted, it was found to be stable even after 6 months. Comparative Example 1 863 parts of the polyol of Example 1 and 137 parts of tolylene/isocyanate were reacted at 100°C for 2 hours to form F- N.C.
:05.0%, viscosity 20,000a-, /20°C prepolymer was prepared. When this was subjected to a cycle test in the same manner as in Example 1, gelation was found. Below, the CPR value of each polyol in each example and comparative example,
The type and amount of acid used in the synthesis of the prepolymer and the storage stability of the obtained prepolymer are collectively indicated. Table-1
以上説明した通り１本発明は、ＣＰＲ５０以下といった
安価な粗製ポリオールを原料として貯蔵安定性の良好な
ＮＧＯプレポリマーを製造するための手段を提供できた
ことにより産業界に貢献しうる。
（以下余白）As explained above, the present invention can contribute to industry by providing a means for producing an NGO prepolymer with good storage stability using an inexpensive crude polyol having a CPR of 50 or less as a raw material. (Margin below)
Claims (1)
ネート化合物を、ＮＣＯ／ＯＨ当量比１．３〜１００で
反応させて末端イソシアネートウレタンプレポリマーを
製造するにあたり、前記ポリオール中のＣＰＲを中和す
るに充分な酸性化合物を添加することを特徴とする貯蔵
安定性の良好な末端イソシアネート基含有ウレタンプレ
ポリマーの製造法。1. When producing a terminal isocyanate urethane prepolymer by reacting a polyol with a CPR of 50 or less and an organic polyisocyanate compound at an NCO/OH equivalent ratio of 1.3 to 100, sufficient acidity to neutralize the CPR in the polyol is required. A method for producing a urethane prepolymer containing terminal isocyanate groups with good storage stability, which comprises adding a compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2098089A JPH03294327A (en) | 1990-04-13 | 1990-04-13 | Production of urethane prepolymer containing terminal isocyanate group and having excellent storage stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2098089A JPH03294327A (en) | 1990-04-13 | 1990-04-13 | Production of urethane prepolymer containing terminal isocyanate group and having excellent storage stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03294327A true JPH03294327A (en) | 1991-12-25 |
Family
ID=14210618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2098089A Pending JPH03294327A (en) | 1990-04-13 | 1990-04-13 | Production of urethane prepolymer containing terminal isocyanate group and having excellent storage stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03294327A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013512210A (en) * | 2009-11-26 | 2013-04-11 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing 1,6-hexanediol |
| JP5484620B1 (en) * | 2013-06-07 | 2014-05-07 | 保土谷化学工業株式会社 | Main agent for polyurethane coating waterproof material and production method thereof, polyurethane coating waterproofing material, polyurethane waterproof coating, and method for reducing free tolylene diisocyanate content |
| JP2014237801A (en) * | 2014-01-14 | 2014-12-18 | 保土谷化学工業株式会社 | Main agent for polyurethane waterproof coating material and manufacturing method thereof, polyurethane waterproof coating material, polyurethane waterproof coating, and method for reducing content of free tolylene diisocyanate |
-
1990
- 1990-04-13 JP JP2098089A patent/JPH03294327A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013512210A (en) * | 2009-11-26 | 2013-04-11 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing 1,6-hexanediol |
| JP5484620B1 (en) * | 2013-06-07 | 2014-05-07 | 保土谷化学工業株式会社 | Main agent for polyurethane coating waterproof material and production method thereof, polyurethane coating waterproofing material, polyurethane waterproof coating, and method for reducing free tolylene diisocyanate content |
| JP2014237758A (en) * | 2013-06-07 | 2014-12-18 | 保土谷化学工業株式会社 | Main agent for polyurethane waterproof coating material and manufacturing method thereof, polyurethane waterproof coating material, polyurethane waterproof coating, and method for reducing content of free tolylene diisocyanate |
| JP2014237801A (en) * | 2014-01-14 | 2014-12-18 | 保土谷化学工業株式会社 | Main agent for polyurethane waterproof coating material and manufacturing method thereof, polyurethane waterproof coating material, polyurethane waterproof coating, and method for reducing content of free tolylene diisocyanate |
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