WO1998014425A1 - Isocyanate derivatives and their production - Google Patents

Isocyanate derivatives and their production Download PDF

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Publication number
WO1998014425A1
WO1998014425A1 PCT/GB1997/002642 GB9702642W WO9814425A1 WO 1998014425 A1 WO1998014425 A1 WO 1998014425A1 GB 9702642 W GB9702642 W GB 9702642W WO 9814425 A1 WO9814425 A1 WO 9814425A1
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WO
WIPO (PCT)
Prior art keywords
isocyanate
bisulphite
sulphite
catalyst
formula
Prior art date
Application number
PCT/GB1997/002642
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French (fr)
Inventor
Andrew Robert Mclauchlin
Original Assignee
University Of Wales, Bangor
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 University Of Wales, Bangor filed Critical University Of Wales, Bangor
Priority to EP97943053A priority Critical patent/EP0929518A1/en
Priority to JP10516308A priority patent/JP2001501617A/en
Priority to AU44670/97A priority patent/AU4467097A/en
Publication of WO1998014425A1 publication Critical patent/WO1998014425A1/en

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Classifications

    • 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
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/14—Compounds containing a carbon atom having four bonds to hetero atoms with a double bond to one hetero atom and at least one bond to a sulfur atom further doubly-bound to oxygen atoms
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484—Polysaccharides and derivatives thereof
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen

Definitions

  • the present invention relates to blocked water-soluble isocyanate compounds.
  • Isocyanates are of particular value in the treatment of plant fibres used as reinforcing materials in synthetic resin composites in that the isocyanates react with the fibre surface in a manner which improves the water resistance of the bond formed between the fibre and the synthetic resin matrix. Moreover the level of modification of the fibre surface can be controlled so as to enable plant fibres to perform as effectively as man-made fibres w hen used as reinforcing materials. It is advantageous, in the early stages of such a treatment, to be able to handle the isocyanate in a water soluble form in which the isocyanate group is blocked with a protecting group and then to remove the protecting group when reaction with the fibre is to take place.
  • existing blocked isocyanates require relativeh high temperatures to remove the blocking group. Furthermore there is the disadvantage that the preparation and handling of such blocked isocyanates involves use of toxic solvents.
  • a method of forming bisulphite adducts of aliphatic isocyanates bearing an aromatic moiety by mixing an aqueous solution of a bisulphite adduct forming agent with a solution of an isocyanate bearing an aromatic moiety in a substituted pyrrolidinone containing a catalytic amount of a substance which catalyses the bisulphite adduct forming reaction, the isocyanate being kept well dispersed so that the adduct is formed as a solution in the aqueous phase.
  • water- soluble blocked aliphatic isocyanates bearing an aromatic moiety may be formed in good yields by reacting aqueous solutions of a adduct forming agent bisulphite with isocyanates dissolved in a substituted pyrrolidinone in the presence of a catalyst such as di-butyl tin chloride.
  • a catalyst such as di-butyl tin chloride.
  • the blocked compounds as produced by the above method can be deblocked at lower temperatures than blocked HDI.
  • the solvent is most preferably an N-substituted pyrrolidinone, most preferably a N-alkyl substituted pyrrolidone. particularly N-alkyl substituted 2-pyrrolidinone.
  • the most preferred solvent for use in the invention is l -methyl-2-pyrrolidinone (also known as N-methyl pyrrolidinone).
  • the bisulphite adduct forming agent may for example be a sulphite, hydrogen sulphite or metabisulphite. most preferably in the form of an alkali metal salt.
  • the preferred alkali metals are sodium and potassium. It is preferred that the bisulphite adduct forming agent is sodium metabisulphite or potassium metabisulphite.
  • the catalyst may for example be an organotin compound, e.g. a dialkyl tin halide.
  • the catalyst is dibutyl tin dichloride.
  • Other catalysts which may be used include l,4-Diazobicyclo[2.2.2
  • the proportions of isocyanate and bisulphite adduct forming agent used for the reaction are preferably such that the ratio of the number of moles of potential sulphite groups present to isocyanate groups is in the range ( 1 -2): 1 (i.e. the number of moles of potential sulphite groups used are equivalent to the number of moles of isocyanate groups or exceed the latter by no more than a twofold excess).
  • the proportions of water and substituted pyrrolidinone should be such that forced precipitation of the metabisulphite does not occur.
  • T iethanolamine (or other amines found to have catalytic action) may be present in a proportion up lo 20% by volume of the reaction mixture.
  • the catalyst is preferably used in an amount up to 0.1% by weight of the total reaction mixture.
  • the amount of catalyst to be used should be such that the yields of the blocked compound are not substantially reduced by virtue of the isocyanate reacting with water present in preference to the metabisulphite.
  • the amount of catalyst to be used in any particular circumstances can be easily determined by routine experimentation so as to secure a satisfactory yield.
  • the reaction is preferably carried out at a temperature not exceeding 15"C. Satisfactory yields are obtained when a temperature of about 5°C is used. Lower temperatures can be used but without any particular advantage and reaction time can be longer.
  • the isocyanate is maintained well dispersed to ensure that the bisulphite adduct is formed as a solution in the aqueous phase. Any conventional method of stirring may be used lo achieve this purpose.
  • the isocyanates to be treated by the method of the invention comprise an aliphatic moiety to which the isocyanate group is bonded and further comprise at least one aromatic moiety.
  • the aliphatic group to which the isocyanate group is bonded may, for example, be a -CMe 2 - group which is also bonded lo an aromatic nucleus.
  • the method of the invention is particularly applicable lo the production of water-soluble forms of m-tetra-rnethylxylene di-isocyanatc (TMXDI) and of alpha- alpha-dimethyl meta-isopropenyl benzyl isocyanate (TMI), both of which can be used in the treatment of plant fibres such as jute. flax, hemp and linseed to improve fibre performance in composite materials.
  • the resin of such a composite material may for example be a phenol-formaldehyde resin or a urea (or urea-melamine) formaldehyde resin.
  • the present invention also includes blocked isocyanates incorporating the groups of formula I or II:
  • Such blocked isocyanate compounds are alkali metal salts more preferably the sodium or potassium salts.
  • the blocked isocyanates of the present invention may be deblocked to free the isocyanate group or groups to react with plant fibres by simply heating to 130 degrees Celsius in the presence of the fibre.
  • one method of treatment consists of soaking the mat in a 25% w/w aqueous solution of adduct. The excess liquid is allowed to drain off and the treated mat dried to a moisture content of about 12% al about 70 degrees Celsius and the mat is then heated while being pressed in a press to a temperature where the blocking group is removed and the isocyanate is free to react with the fibre surface.
  • the compound shown in formula I (blocked TMXDI) was prepared in the following manner: Sodium metabisulphite (190g) was dissolved in 530g of water. The clear solution obtained was placed in a flask provided with a stirrer and cooling means.

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

Abstract

This invention describes a method of forming bisulphite adducts of aliphatic isocyanates bearing an aromatic moiety by mixing an aqueous solution of a bisulphite adduct forming agent with a solution of an isocyanate bearing an aromatic moiety in a substituted pyrrolidinone containing a catalytic amount of a substance which catalyses the bisulphite adduct forming reaction, the isocyanate being kept well dispersed so that the adduct is formed as a solution in the aqueous phase.

Description

ISOCYANATE DERIVATIVES AND THEIR PRODUCTION
The present invention relates to blocked water-soluble isocyanate compounds.
Isocyanates are of particular value in the treatment of plant fibres used as reinforcing materials in synthetic resin composites in that the isocyanates react with the fibre surface in a manner which improves the water resistance of the bond formed between the fibre and the synthetic resin matrix. Moreover the level of modification of the fibre surface can be controlled so as to enable plant fibres to perform as effectively as man-made fibres w hen used as reinforcing materials. It is advantageous, in the early stages of such a treatment, to be able to handle the isocyanate in a water soluble form in which the isocyanate group is blocked with a protecting group and then to remove the protecting group when reaction with the fibre is to take place. However, existing blocked isocyanates require relativeh high temperatures to remove the blocking group. Furthermore there is the disadvantage that the preparation and handling of such blocked isocyanates involves use of toxic solvents.
Thus, for example. Guise (Λust. .1. Chem.. 25:2583-2595( 1972)) has described the reaction of isocyanates with sodium or potassium metabisulphite to form blocked isocyanates in aqueous 1.4-dioxane alone or in admixture with other solvents. The preparation of a blocked form of 1.6-hexamethylene diisocyanate ( HDI) is described and this compound requires a temperature of 167"C lo enable the isocyanate groups to be unblocked.
According to the invention, therefore, there is provided a method of forming bisulphite adducts of aliphatic isocyanates bearing an aromatic moiety by mixing an aqueous solution of a bisulphite adduct forming agent with a solution of an isocyanate bearing an aromatic moiety in a substituted pyrrolidinone containing a catalytic amount of a substance which catalyses the bisulphite adduct forming reaction, the isocyanate being kept well dispersed so that the adduct is formed as a solution in the aqueous phase.
We have found, and this forms the basis of the present invention, that water- soluble blocked aliphatic isocyanates bearing an aromatic moiety may be formed in good yields by reacting aqueous solutions of a adduct forming agent bisulphite with isocyanates dissolved in a substituted pyrrolidinone in the presence of a catalyst such as di-butyl tin chloride. This process avoids the u.se of 1 ,4-dioxane which is difficult to use on a large scale because of the precautions required to protect those carrying out reactions with such a solvent.
The blocked compounds as produced by the above method can be deblocked at lower temperatures than blocked HDI.
The solvent is most preferably an N-substituted pyrrolidinone, most preferably a N-alkyl substituted pyrrolidone. particularly N-alkyl substituted 2-pyrrolidinone. The most preferred solvent for use in the invention is l -methyl-2-pyrrolidinone (also known as N-methyl pyrrolidinone).
The bisulphite adduct forming agent may for example be a sulphite, hydrogen sulphite or metabisulphite. most preferably in the form of an alkali metal salt. The preferred alkali metals are sodium and potassium. It is preferred that the bisulphite adduct forming agent is sodium metabisulphite or potassium metabisulphite.
The catalyst may for example be an organotin compound, e.g. a dialkyl tin halide. Preferably the catalyst is dibutyl tin dichloride. Other catalysts which may be used include l,4-Diazobicyclo[2.2.2 |octane (DABCO) as well as secondary and tertiary amines. It is preferred that the reaction be conducted in the presence of triethanolamine which, we have found, improves the yield of the bisulphite addition product, possibly by acting as a co-solvent to introduce the isocyanate to the aqueous phase of the mixture. Other co-solvents may be used for this purpose.
The proportions of isocyanate and bisulphite adduct forming agent used for the reaction are preferably such that the ratio of the number of moles of potential sulphite groups present to isocyanate groups is in the range ( 1 -2): 1 (i.e. the number of moles of potential sulphite groups used are equivalent to the number of moles of isocyanate groups or exceed the latter by no more than a twofold excess).
The proportions of water and substituted pyrrolidinone should be such that forced precipitation of the metabisulphite does not occur. T iethanolamine (or other amines found to have catalytic action) may be present in a proportion up lo 20% by volume of the reaction mixture.
The catalyst is preferably used in an amount up to 0.1% by weight of the total reaction mixture.
The amount of catalyst to be used should be such that the yields of the blocked compound are not substantially reduced by virtue of the isocyanate reacting with water present in preference to the metabisulphite. The amount of catalyst to be used in any particular circumstances can be easily determined by routine experimentation so as to secure a satisfactory yield.
The reaction is preferably carried out at a temperature not exceeding 15"C. Satisfactory yields are obtained when a temperature of about 5°C is used. Lower temperatures can be used but without any particular advantage and reaction time can be longer. To carry out the method of the invention, the isocyanate is maintained well dispersed to ensure that the bisulphite adduct is formed as a solution in the aqueous phase. Any conventional method of stirring may be used lo achieve this purpose.
The isocyanates to be treated by the method of the invention comprise an aliphatic moiety to which the isocyanate group is bonded and further comprise at least one aromatic moiety. The aliphatic group to which the isocyanate group is bonded may, for example, be a -CMe2- group which is also bonded lo an aromatic nucleus.
The method of the invention is particularly applicable lo the production of water-soluble forms of m-tetra-rnethylxylene di-isocyanatc (TMXDI) and of alpha- alpha-dimethyl meta-isopropenyl benzyl isocyanate (TMI), both of which can be used in the treatment of plant fibres such as jute. flax, hemp and linseed to improve fibre performance in composite materials. The resin of such a composite material may for example be a phenol-formaldehyde resin or a urea (or urea-melamine) formaldehyde resin.
The present invention also includes blocked isocyanates incorporating the groups of formula I or II:
Figure imgf000006_0001
Formula I Formula II Preferably such blocked isocyanate compounds are alkali metal salts more preferably the sodium or potassium salts.
The blocked isocyanates of the present invention may be deblocked to free the isocyanate group or groups to react with plant fibres by simply heating to 130 degrees Celsius in the presence of the fibre. In the case of a pre-formed mat of plant fibres such as jute, one method of treatment consists of soaking the mat in a 25% w/w aqueous solution of adduct. The excess liquid is allowed to drain off and the treated mat dried to a moisture content of about 12% al about 70 degrees Celsius and the mat is then heated while being pressed in a press to a temperature where the blocking group is removed and the isocyanate is free to react with the fibre surface.
The following Examples illustrates but do not limit the invention:
Example 1
The compound shown in formula I (blocked TMXDI) was prepared in the following manner: Sodium metabisulphite (190g) was dissolved in 530g of water. The clear solution obtained was placed in a flask provided with a stirrer and cooling means.
l-Methyl-2-pyrroIidinone (200g) was added to the solution along with 120g of m tetramethylxylene di-isocyanate. 3.5g of triethanolamine and O. l g of dibutyl tin dichloride. The mixture was maintained at 5 degrees Celsius with continued stirring for seven days at which time the reaction mixture had become one aqueous suspension. After filtering this mixture, the residue contained the desired blocked isocyanate and the filtrate, after evaporating and adding excess acetone yielded a further crop of blocked isocyanate. The combined yield was 1 80g of the sodium salt of the blocked isocyanate. Example 2
The compound shown in formula II (blocked TMI) w as prepared in the following manner: Sodium metabisulphite ( 1 g) was dissolved in water (53g) lo give a clear solution. To this was added l -methyl-2-pyrrolidinone (20g). dimethyl-m- isopropenyl benzyl isocyanate (TMI. 9.4g). triethanolamine (3.0g) and O. l dibutyl tin dichloride. The mixture was stirred vigorously for seven days al 5"C alter which the mixture consisted of a cloudy suspension. The product was separated from the cloudy suspension using the same steps as in example 1 , and l Og of blocked dimethyl-m- isopropenyl benzyl isocyanate of the formula II were obtained.

Claims

1. A method of forming bisulphite adducts of aliphatic isocyanates bearing an aromatic moiety by mixing an aqueous solution of a bisulphite adduct forming agent with a solution of an isocyanate bearing an aromatic moiety in a substituted pyrrolidinone containing a catalytic amount of a substance which catalyses the bisulphite adduct forming reaction, the isocyanate being kept well dispersed so that the adduct is formed as a solution in the aqueous phase.
2. A method as claimed in claim I wherein the solvent is an N-substituted pyrrolidinone.
3. A method as claimed in claim 2 wherein the solvent is an N-alkyl substituted pyrrolidinone.
4. A method as claimed in claim 3 wherein the solvent is N-methyl pyrrolidinone.
5. A method as claimed in any one of claims 1 to 4 w herein the catalyst is an organotin compound.
6. A method as claimed in claim 5 wherein the catalyst is a dialkyl tin halide.
7. A method as claimed in claim 6 wherein the catalyst is dibutyl tin chloride.
8. A method as claimed in any one of claims 1 to 4 wherein the catalyst is DABCO.
9. A method as claimed in any one of claims 1 to 8 conducted in the presence of triethanolamine.
10. A method as claimed in any one of claims I lo 9 w herein the bisulphite adduct forming agent is a sulphite, hydrogen sulphite or metabisulphite.
1 1. A method as claimed in claim 10 wherein the bisulphite adduct forming agent is an alkali metal sulphite, hydrogen sulphite or mclabisulphite.
12. A method as claimed in claim 1 1 wherein the alkali metal is sodium or potassium.
13. A method as claimed in claim 12 wherein the bisulphite adduct forming agent is sodium metabisulphite or potassium metabisulphite.
14. A method as claimed in any one of claims 1 to 13 wherein the isocyanate comprises an isocyanate group bonded to an aromatic moiety by a -CMe2-group.
15. A method as claimed in claim 14 wherein the isocyanate is TMI or TMXDI.
16. A method as claimed in any one l^ claims 1 to 1 5 w herein the ratio of the number of moles of potential sulphite groups present to isocyanate groups is in the range (1-2):1.
17. A blocked isocyanate incorporating the group of the formula I
Figure imgf000010_0001
Formula T
18. A blocked isocyanate incorporating the group of the formula II
Figure imgf000011_0001
Formula II
19. A blocked isocyanate compound as claimed in claim 16 or 1 7 which is an alkali metal salt.
20. A blocked isocyanate as claimed in claim 19 wherein the alkali metal is sodium or potassium.
PCT/GB1997/002642 1996-10-01 1997-10-01 Isocyanate derivatives and their production WO1998014425A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP97943053A EP0929518A1 (en) 1996-10-01 1997-10-01 Isocyanate derivatives and their production
JP10516308A JP2001501617A (en) 1996-10-01 1997-10-01 Isocyanate derivative and its production
AU44670/97A AU4467097A (en) 1996-10-01 1997-10-01 Isocyanate derivatives and their production

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9620459.9A GB9620459D0 (en) 1996-10-01 1996-10-01 Improvements in or relating to blocked isocyanates and their production
GB9620459.9 1996-10-01

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WO1998014425A1 true WO1998014425A1 (en) 1998-04-09

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EP (1) EP0929518A1 (en)
JP (1) JP2001501617A (en)
KR (1) KR20000048790A (en)
AU (1) AU4467097A (en)
GB (1) GB9620459D0 (en)
WO (1) WO1998014425A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451101B1 (en) 2000-12-29 2002-09-17 Basf Corporation Parting agent for an isocyanate wood binder
US6458238B1 (en) 2000-12-29 2002-10-01 Basf Corporation Adhesive binder and synergist composition and process of making lignocellulosic articles
US6464820B2 (en) 2000-12-29 2002-10-15 Basf Corporation Binder resin and synergist composition including a parting agent and process of making lignocellulosic
WO2003106504A1 (en) 2002-06-18 2003-12-24 Pasqua Anna Oreste Epimerized derivatives of k5 polysaccharide with a very high degree of sulfation
EP2415879A1 (en) * 2010-08-06 2012-02-08 LANXESS Deutschland GmbH Compositions comprising at least one compound containing carbamoylsulfonate groups and their use as tanning agents
EP2508626A1 (en) * 2011-04-04 2012-10-10 LANXESS Deutschland GmbH Solid, particular tanning agent preparations
EP2508627A1 (en) * 2011-04-04 2012-10-10 LANXESS Deutschland GmbH Solid, particular material on the basis of compounds containing carbamoylsulfonate groups
CN104640901A (en) * 2012-09-18 2015-05-20 大荣产业株式会社 Blocked polyisocyanate composition, prepolymer composition and method of manufacturing said compositions, and thermally dissociable blocking agent of blocked polyisocyanate composition

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Publication number Priority date Publication date Assignee Title
JP5307308B1 (en) * 2012-09-18 2013-10-02 大榮産業株式会社 Block polyisocyanate composition, prepolymer composition and production method thereof, and thermally dissociable blocking agent for block polyisocyanate composition

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2307563A1 (en) * 1972-02-18 1973-08-23 Commw Scient Ind Res Org BISULPHITE ADDITIONAL PRODUCT AND METHOD FOR ITS MANUFACTURING

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2307563A1 (en) * 1972-02-18 1973-08-23 Commw Scient Ind Res Org BISULPHITE ADDITIONAL PRODUCT AND METHOD FOR ITS MANUFACTURING

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451101B1 (en) 2000-12-29 2002-09-17 Basf Corporation Parting agent for an isocyanate wood binder
US6458238B1 (en) 2000-12-29 2002-10-01 Basf Corporation Adhesive binder and synergist composition and process of making lignocellulosic articles
US6464820B2 (en) 2000-12-29 2002-10-15 Basf Corporation Binder resin and synergist composition including a parting agent and process of making lignocellulosic
US6638459B2 (en) 2000-12-29 2003-10-28 Basf Corporation Process of making lignocellulosic articles
US6649098B2 (en) 2000-12-29 2003-11-18 Basf Corporation Process of making lignocellulosic articles
WO2003106504A1 (en) 2002-06-18 2003-12-24 Pasqua Anna Oreste Epimerized derivatives of k5 polysaccharide with a very high degree of sulfation
EP2415879A1 (en) * 2010-08-06 2012-02-08 LANXESS Deutschland GmbH Compositions comprising at least one compound containing carbamoylsulfonate groups and their use as tanning agents
WO2012016907A1 (en) * 2010-08-06 2012-02-09 Lanxess Deutschland Gmbh Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents
US9376729B2 (en) 2010-08-06 2016-06-28 Lanxess Deutschland Gmbh Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents
CN103080341B (en) * 2010-08-06 2015-11-25 朗盛德国有限责任公司 Comprise at least one containing the composition of compound of formamyl sulfonate ester group and the purposes as tanning agent thereof
US20130288066A1 (en) * 2010-08-06 2013-10-31 Lanxess Deutschland Gmbh Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents
KR101439070B1 (en) 2010-08-06 2014-09-05 란세스 도이치란트 게엠베하 Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents
CN103080341A (en) * 2010-08-06 2013-05-01 朗盛德国有限责任公司 Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents
WO2012136559A1 (en) 2011-04-04 2012-10-11 Lanxess Deutschland Gmbh Solid, particulate material based on compounds containing carbamoylsulfonate groups
CN103502477A (en) * 2011-04-04 2014-01-08 朗盛德国有限责任公司 Solid, particulate material based on compounds containing carbamoylsulfonate groups
US20140123399A1 (en) * 2011-04-04 2014-05-08 Lanxess Deutschland Gmbh Solid, particulate tanning agent preparations
WO2012136565A1 (en) 2011-04-04 2012-10-11 Lanxess Deutschland Gmbh Solid, particulate tanning agent preparations
EP2508627A1 (en) * 2011-04-04 2012-10-10 LANXESS Deutschland GmbH Solid, particular material on the basis of compounds containing carbamoylsulfonate groups
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AU4467097A (en) 1998-04-24
KR20000048790A (en) 2000-07-25
GB9620459D0 (en) 1996-11-20
EP0929518A1 (en) 1999-07-21
JP2001501617A (en) 2001-02-06

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