WO2007116761A1 - Composition contenant de l'isocyanate de diphenylmethane - Google Patents

Composition contenant de l'isocyanate de diphenylmethane Download PDF

Info

Publication number
WO2007116761A1
WO2007116761A1 PCT/JP2007/056466 JP2007056466W WO2007116761A1 WO 2007116761 A1 WO2007116761 A1 WO 2007116761A1 JP 2007056466 W JP2007056466 W JP 2007056466W WO 2007116761 A1 WO2007116761 A1 WO 2007116761A1
Authority
WO
WIPO (PCT)
Prior art keywords
acidity
mass
weeks
diphenylmethane
viscosity
Prior art date
Application number
PCT/JP2007/056466
Other languages
English (en)
Japanese (ja)
Inventor
Takeo Takeda
Tatsuya Yamaguchi
Tomomitsu Yoshihara
Susumu Yamada
Yoshiyuki Kanbara
Original Assignee
Nippon Polyurethane Industry Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Polyurethane Industry Co., Ltd. filed Critical Nippon Polyurethane Industry Co., Ltd.
Priority to JP2008509786A priority Critical patent/JPWO2007116761A1/ja
Publication of WO2007116761A1 publication Critical patent/WO2007116761A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/18—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/089—Reaction retarding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups

Definitions

  • the present invention relates to a diphenylmethane-based isocyanate composition that can be used in the production of various polyurethane products.
  • diphenylmethane isocyanate compositions having a predetermined acidity may be used.
  • the diphenylmethane-based isocyanate composition having the predetermined acidity is preferable as a raw material for, for example, rigid polyurethane foam.
  • the "acidity” here means a value obtained by converting an acid component that reacts with alcohol at room temperature and liberated into hydrogen chloride, and is measured in accordance with JIS K-1603 (1985). . The same applies hereinafter.
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-220137
  • the diphenylmethane isocyanate composition disclosed in Patent Document 1 can reduce the variation in acidity by intentionally setting the acidity to a predetermined value, but it can be stored over time. It seems that the stability, especially the storage stability at high temperature such as 45 ° C-constant atmosphere, deteriorates (viscosity increases (thickening)) and tends to increase.
  • Such a thickening of dimethane methane isocyanate causes problems in the production of polyurethane resin. For example, when the user and the manufacturer are at a long distance, the diphenylmethane isocyanate composition thickens due to the passage of a certain period during transportation, or the period when the diphenylmethane isocyanate yarn and the composition start to be used suddenly. Is extended When this thickened diphenylmethane isocyanate composition is used for the production of polyurethane resin, the mixing with polyols becomes non-uniform and the reactivity is increased. It may not be possible to produce a desired polyurethane product, such as non-uniformity (variability in reactivity).
  • an object of the present invention is to provide a diphenylmethane isocyanate composition having a longer period of time for thickening than the conventional one (high storage stability).
  • the present invention includes a composition obtained by adding an alkylchlorosilane having a total carbon number of ⁇ 24 in a molecular structure to a diphenylmethane isocyanate having an acidity of less than 0.1% by mass. It is a diphenylmethane isocyanate composition having a high acidity and an acidity of at least mass%.
  • the alkylchlorosilane is preferably 1,3-dichlorotetraisopropyldisiloxane or triethylchlorosilane.
  • the diphenylmethane isocyanate composition according to the present embodiment is obtained by adding an alkylchlorosilane having a total carbon number power of -24 in a molecular structure to a diphenylmethane isocyanate having an acidity of less than 0.1% by mass. And a high acidity composition having an acidity of 0.1% by mass or more.
  • Diphenylmethane isocyanate is a mixture of dinuclear MDI (diphenylmethane isocyanate) and trinuclear or higher polynuclear (MDI condensate) (polyphenylene polymethylene polyisocyanate). It is.
  • This diphenylmethane isocyanate can be obtained by converting the amino group of a condensation mixture (polyamine) obtained by the condensation reaction of aline and formalin to an isocyanate group by phosgene or the like. By changing the composition ratio of the raw materials and the reaction conditions during condensation, the final diphenol The composition of tan-based isocyanate (nuclear distribution and isomer composition ratio) can be controlled.
  • diphenylmethane-based isocyanate is used for reaction conditions and separation conditions such as the reaction liquid after conversion to isocyanate group, the reaction liquid power is also removed from the solvent, and the bottom is partially distilled off from MDI. It may be a mixture of several different types. Further, commercially available diphenylmethane isocyanate may be mixed with MDI.
  • the proportion of MDI in the dimethane methane isocyanate is preferably 20 to 80%, more preferably 40 to 60%.
  • the ratio of MDI here is the ratio for which the peak area specific power of MDI by GPC (gel permeation chromatography) is also obtained.
  • MDI which is a binuclear body, is composed of three isomers: 4, 4'- MDI, 2, 2'- MDI, and 2, 4'- MDI.
  • the composition ratio of isomers can be determined from a calibration curve based on the area percentage of each peak obtained by GC (gas chromatography).
  • the average number of functional groups of the diphenylmethane isocyanate is preferably 2.2 or more, more preferably 2.2 to 3.1. Further, the isocyanate group content of diphenylmethane-based isocyanate is preferably 28 to 33% by mass, more preferably 28.5 to 32.5% by mass.
  • the acidity of the diphenylmethane isocyanate having an acidity of less than 0.1% by mass used in the present invention is preferably a diphenylmethane isocyanate (low acidity product) that is generally at the above-mentioned acidity level. In view of the above, it is preferably 0.05% by mass or less, more preferably 0.03% by mass or less.
  • the total number of carbon atoms in the alkyl chlorosilane having a total carbon number in the molecular structure to 24 is the total number of carbon atoms of the alkyl group or the alkyl group and alkylene group bonded to the silicon atom which may be plural.
  • the total number of carbons in triethylchlorosilane is 6, and the total number of carbons in 1,3-dichlorotetraisopropyldisiloxane is 12.
  • alkyl chlorosilanes having a total carbon number power of -24 in the molecular structure are listed below.
  • a compound in which three chlorine atoms and one saturated hydrocarbon group are bonded to one silicon atom in the molecular structure such as n-butyltrichlorosilane, isobutyltrichlorosilane, pentyl Rutrichlorosilane, hexyltrichlorosilane, cyclohexyltrichlorosilane, heptyltrichlorosilane, octyltrichlorosilane, nonyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, tetradecyltrichlorosilane, octadecyltrichlorosilane, eico Siltrichlorosilane, etc.
  • a compound in which one chlorine and three saturated hydrocarbon groups are bonded to one silicon in the molecular structure for example, triethylchlorosilane, tripropylchlorosilane, tributylchlorosilane, trihexylchlorosilane, Dimethylpropylchlorosilane, dimethylisopropylchlorosilane, tert-butyldimethylchlorosilane, dimethyloctylchlorosilane, dimethyloctadecylchlorosilane, etc.
  • a compound in which one chlorine and two saturated hydrocarbon groups are bonded to each of two silicons having siloxane bonds in the molecular structure for example, 1, 1, 3, 3-tetramethyl-1, 3-dichlorodichlorosiloxane, 1,3-dichlorotetraisopropyldisiloxane, etc.
  • a compound in which two chlorine atoms and one saturated hydrocarbon group are bonded to each of two silicon atoms alkylene-bonded in the molecular structure for example, 1,2-bis (methyldichlorosilyl) ethane etc,
  • a compound in which one chlorine and two saturated hydrocarbon groups are bonded to each of two silicon atoms alkylene-bonded in the molecular structure for example, 1,2-bis (dimethylchlorosilyl) ethane Etc.
  • diphenylmethane isocyanate a mixture of two or more of the above examples of alkylchlorosilane may be used.
  • Example [0022] In all the examples and all the comparative examples, the diphenylmethane isocyanate shown below having a low acidity was prepared as the diphenylmethane isocyanate used.
  • NCO content in the following tables and all comparative examples, and “NCO% (mass%)” in the table below. It measured by the measuring method shown.
  • the end point of the titration is the point at which the blue color of promofenol blue indicator turns yellow
  • NCO content [(BA) X 42 X 0.5 X f] X 100 ⁇ (SX 1000) In the above formula,
  • Viscosities in all Examples and all Comparative Examples were measured by a method according to JIS K2283 (1980) using a Cannon Fenceke viscometer. The outline of the measurement method is as follows.
  • V C X t
  • NCO content of the above diphenylmethane isocyanate having an acidity of 0.011% by mass
  • rate of change with time in viscosity was measured at 45 ° C in a constant atmosphere. The results are shown in Table 3 below.
  • Dichloromethane isocyanate composition prepared by adding 2.85 g of isophthalic acid dichloride to 500 g of the above diphenylmethane isocyanate having an acidity of 0.011% by mass and adjusting the acidity to 0.249% by mass. Then, the NCO content after the preparation and the rate of change with time of the viscosity (from 0 weeks to 6 weeks every week) were measured at 45 ° C in a constant atmosphere. The results are shown in Table 8 below.
  • Against acidity 0.011 wt% a is said Jifueerumetan system Isoshianeto 500 g, terephthalic acid dichloride 2. 85g ⁇ Ka ⁇ , Jifue was adjusted acidity to 0.210 mass 0/0 - Rumetan based Isoshianeto composition After the preparation, the NCO content and the rate of change with time of the viscosity (from 0 to 6 weeks per week) were measured at 45 ° C in a constant atmosphere. The results are shown in Table 10 below.
  • Tables 1, 2 and 5 ⁇ From LO, the rate of change with time of viscosity can be suppressed for up to about 4 weeks even in Comparative Examples 3-8 (see Comparative Example 5). It can be seen that the diphenylmethane isocyanate composition can suppress the rate of change with time of viscosity for a longer period (up to about 6 weeks).
  • Diphenylmethane isocyanate composition in which 5.3-Og of 1,3-dichlorotetraisopropyldisiloxane is added to 500 g of the above diphenylmethane isocyanate having an acidity of 0.011% by mass to adjust the acidity to 0.252% by mass. Measure the viscosity of the film after the preparation (0 days, 7 days, 14 days, 21 days, 42 hours, 80 hours) at 45 ° C in a constant atmosphere. did. The results are shown in Table 12 below.
  • the results are shown in Table 15 below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une composition à base d'isocyanate de diphénylméthane comprenant une composition obtenue par ajout d'un alkylchlorosilane dont la structure moléculaire comporte un total de 4 à 24 atomes de carbone à un isocyanate de diphénylméthane ayant un taux d'acide inférieur à 0,1 % en masse. Ladite composition d'isocyanate de diphénylméthane présente un taux d'acide élevé supérieur ou égal à 0,1 % en masse. L'alkylchlorosilane est de préférence le 1,3-dichlorotétraisopropyldisiloxane ou le triéthylchlorosilane. La viscosité de la composition d'isocyanate de diphénylméthane de l'invention ne commence à augmenter que plus tardivement que celle des compositions classiques ; en d'autres termes, la composition de l'invention offre une plus grande stabilité au stockage.
PCT/JP2007/056466 2006-03-30 2007-03-27 Composition contenant de l'isocyanate de diphenylmethane WO2007116761A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008509786A JPWO2007116761A1 (ja) 2006-03-30 2007-03-27 ジフェニルメタン系イソシアネート組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006094693 2006-03-30
JP2006-094693 2006-03-30

Publications (1)

Publication Number Publication Date
WO2007116761A1 true WO2007116761A1 (fr) 2007-10-18

Family

ID=38581058

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/056466 WO2007116761A1 (fr) 2006-03-30 2007-03-27 Composition contenant de l'isocyanate de diphenylmethane

Country Status (3)

Country Link
JP (1) JPWO2007116761A1 (fr)
CN (1) CN101415671A (fr)
WO (1) WO2007116761A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009057310A1 (fr) * 2007-11-02 2009-05-07 Nippon Polyurethane Industry Co., Ltd. Composition de résine de polyuréthane pouvant durcir par réaction et adhésif de polyuréthane à deux composants pouvant durcir par réaction fait à l'aide de cette composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05117220A (ja) * 1991-04-06 1993-05-14 Bayer Ag 有機イソシアネートの状態調整および／または精製方法
JPH05194353A (ja) * 1991-07-23 1993-08-03 Bayer Ag ポリイソシアネートの精製方法、このように精製されたポリイソシアネートおよびそれの使用
JPH0625382A (ja) * 1992-02-28 1994-02-01 Mitsubishi Kasei Dow Kk ポリイソシアネート組成物
JPH0625381A (ja) * 1992-02-28 1994-02-01 Mitsubishi Kasei Dow Kk ポリイソシアネート組成物

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4117384A1 (de) * 1991-05-28 1992-12-03 Bayer Ag Verfahren zur herstellung fluessiger, lagerstabiler carbodiimid- und/oder uretonimingruppen aufweisender organischer isocyanate und ihre verwendung zur herstellung von polyurethankunststoffen
DE4217525A1 (de) * 1992-05-27 1993-12-02 Bayer Ag Verfahren zur Standardisierung und Stabilisierung von organischen Polyisocyanaten und ihre Verwendung
JP4247735B2 (ja) * 2002-09-10 2009-04-02 日本ポリウレタン工業株式会社 ポリメチレンポリフェニレンポリイソシアネートの着色低減方法
DE102004005319A1 (de) * 2004-02-04 2005-08-25 Bayer Materialscience Ag Verfahren zur Herstellung von hochreinem 2,4'-Methylendiphenyldiisocyanat
DE102004005320A1 (de) * 2004-02-04 2005-08-25 Bayer Materialscience Ag Herstellung von Di- und Polysocyanaten der Diphenylmethanreihe mit definierter Acidität
FR2880021B1 (fr) * 2004-12-23 2007-02-09 Rhodia Chimie Sa Compositions isocyanates presentant de bonnes proprietes de melange et utilisation de derives silyles comme adjuvants de compositions isocyanates, notamment de melange

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05117220A (ja) * 1991-04-06 1993-05-14 Bayer Ag 有機イソシアネートの状態調整および／または精製方法
JPH05194353A (ja) * 1991-07-23 1993-08-03 Bayer Ag ポリイソシアネートの精製方法、このように精製されたポリイソシアネートおよびそれの使用
JPH0625382A (ja) * 1992-02-28 1994-02-01 Mitsubishi Kasei Dow Kk ポリイソシアネート組成物
JPH0625381A (ja) * 1992-02-28 1994-02-01 Mitsubishi Kasei Dow Kk ポリイソシアネート組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009057310A1 (fr) * 2007-11-02 2009-05-07 Nippon Polyurethane Industry Co., Ltd. Composition de résine de polyuréthane pouvant durcir par réaction et adhésif de polyuréthane à deux composants pouvant durcir par réaction fait à l'aide de cette composition
JP2009114258A (ja) * 2007-11-02 2009-05-28 Nippon Polyurethane Ind Co Ltd 反応硬化型ポリウレタン樹脂組成物、及び該組成物を用いた二液反応硬化型ポリウレタン接着剤

Also Published As

Publication number Publication date
JPWO2007116761A1 (ja) 2009-08-20
CN101415671A (zh) 2009-04-22

Similar Documents

Publication Publication Date Title
TW593394B (en) Clear, resilient polyurethane elastomers
TWI239967B (en) Polyether polyurethane and urethane prepolymer
TWI535812B (zh) 自交聯聚矽氧壓感性黏著劑組合物，其製造方法及由其製得之物件
JP6466950B2 (ja) ポリオール
JPS633029A (ja) オルガノポリシロキサン−ポリ尿素ブロックコポリマ−およびその製造方法
CN105793327B (zh) 金属化的多面体低聚倍半硅氧烷催化剂组合物的合成及用途
CN103068872A (zh) 不含锡的甲硅烷基-封端的聚合物
WO2011123351A1 (fr) Mélange de polyuréthane silylé contenant du polydiorganosiloxane et du polyuréthane silylé et substrats contenant celui-ci et procédé de fabrication desdits substrats
JP2016540071A (ja) カルダノール変性エポキシポリオール
CN104448205B (zh) 一种水性聚氨酯、其制备方法及其用于涂饰剂的应用
KR20100047293A (ko) 실리콘-함유 폼
JP7552602B2 (ja) ウレタン樹脂
WO2008023690A1 (fr) Formule de diphénylméthane-isocyanate modifiée par uréthane
WO2008012908A1 (fr) Procédé de fabrication de mousse de polyuréthane
CN114196215B (zh) 一种mtq硅树脂、其制备方法、含氟有机硅橡胶及其制备方法和应用
WO2011161011A1 (fr) Matériaux basés sur un isocyanate fonctionnalisé par alkoxysilane
CN107109063A (zh) 包含聚酰胺和聚硅氧烷的热塑性组合物
JP2006057093A (ja) シラン末端のポリエーテルをベースとする組成物及びその使用
WO2007116761A1 (fr) Composition contenant de l'isocyanate de diphenylmethane
CN104428336A (zh) 可再生来源的聚酯-聚氨酯弹性体
CN105073923A (zh) 胺封端的基本上线性的硅氧烷化合物以及由其制备的环氧产品
CN106432687A (zh) 低密度镜面聚氨酯微孔弹性体用树脂及应用方法
CN109575293A (zh) 一种高聚合度主链型聚醚改性有机硅匀泡剂的制备方法
TWI544008B (zh) Method for producing polysiloxane
US9334236B2 (en) Lactam-based compounds with a urethane or urea functional group, and uses thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07739904

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2008509786

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 200780012333.4

Country of ref document: CN

122 Ep: pct application non-entry in european phase

Ref document number: 07739904

Country of ref document: EP

Kind code of ref document: A1