EP0000096A1 - Method for the manufacture of amino-formaldehyde resins - Google Patents
Method for the manufacture of amino-formaldehyde resins Download PDFInfo
- Publication number
- EP0000096A1 EP0000096A1 EP78300026A EP78300026A EP0000096A1 EP 0000096 A1 EP0000096 A1 EP 0000096A1 EP 78300026 A EP78300026 A EP 78300026A EP 78300026 A EP78300026 A EP 78300026A EP 0000096 A1 EP0000096 A1 EP 0000096A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- resin
- formaldehyde
- amino
- reaction
- reactive modifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920005989 resin Polymers 0.000 title claims abstract description 75
- 239000011347 resin Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 29
- ZHNUHDYFZUAESO-OUBTZVSYSA-N aminoformaldehyde Chemical compound N[13CH]=O ZHNUHDYFZUAESO-OUBTZVSYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003607 modifier Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- -1 amino compound Chemical class 0.000 claims abstract description 8
- 238000009877 rendering Methods 0.000 claims abstract description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000004202 carbamide Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 235000013877 carbamide Nutrition 0.000 description 14
- 238000007792 addition Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LHZGEGQZBPULEQ-UHFFFAOYSA-N 3,5-bis(methoxymethyl)-1,3,5-oxadiazinan-4-one Chemical compound COCN1COCN(COC)C1=O LHZGEGQZBPULEQ-UHFFFAOYSA-N 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 150000005217 methyl ethers Chemical class 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
Definitions
- This invention relates to the manufacture of resins, and in particular the manufacture of aminoformaldehyde resins,
- Amino-formaldehyde resins are manufactured on a large scale and used in moulding powders, foams for cavity wall insulation etc, for adhesives and in textile finishing.
- the most commonly used amino compounds are urea and melamine and their derivatives.
- aminoformaldehyde resins such as urea-formaldehyde or melamine-formaldehyde resins
- urea-formaldehyde or melamine-formaldehyde resins The usual commercial method for the manufacture of aminoformaldehyde resins is to react the amino compound and formaldehyde in an aqueous system at a temperature of 60 to 90°C.
- foams of superior resilience may be produced from resins of low water content as described in our UK Patent Application No.51269/77.
- the end product is a material containing a high proportion of glycol which has totally unsatisfactory properties when considered as replacement for modern urea-formaldehyde or melamine-formaldehyde resins.
- the present invention is thus concerned with the problem of providing a process for the preparation of amino- formaldehyde resins of lower water content than by the conventional aqueous system, yet avoiding the difficulties of solid phase reaction.
- the products so made are useful resins, but the reactive modifiers described are compounds which not only modify the reaction system to the liquid phase at the reaction temperature, but also modify the properties of the resulting resin from those of a simple urea-or melamine-formaldehyde resin.
- the present invention has as its primary objective the preparation of amino-formaldehyde resin of lower water content than those obtained by the conventional aqueous system, whilst avoiding the need to use compounds which will modify the properties of the resin produced.
- a method for the manufacture of an aminoformaldehyde resin comprises reacting an amino compound with formaldehyde or paraformaldehyd in the liquid phase characterized in that said compounds are reacted in the presence of a reactive modifier to ensure said liquid phase, said modifier comprising an aminoformaldehyde resin capable of reaction with further monomers, and which is capable of rendering the mixture of reactants liquid at least at the temperature at which the reaction is to be carried out.
- the reaction is preferably carried out at a temperature above 60°C and more preferably in the range 70 C to 115°C.
- water may be omitted, or if added, the amount of water present in the reaction mixture (excluding water formed in the condensation reaction) is preferably less than 6% by weight of the total mixture.
- low molecular weight liquid resins of low water content are not freely available to use as starting materials at the present time.
- a high solids content aqueous solution of a reactant resin i.e. one capable of reacting with further monomers
- the end product when using such a modifier is of lower water content than the products of the usual method of producing such resins.
- these products could be used as reactive modifiers in turn, with a correspondingly lower water content in the reaction mixture.
- the reactive modifier i.e. the initial aminoformaldehyde resin; will, when the reaction is completed, form part of the resin produced.
- the function of the reactive modifier in the method of this invention is to render the reactant mixture a liquid at the temperature of reaction so that the reaction can be carried out in a liquid phase.
- the aminoformaldehyde resin used as reactive modifier may be a resin containing the same monomers in the same ratio as the resin being manufactured. However, this . need not necessarily be the case and the reactive modifier resin may contain different proportions of monomers, and/or additional or different monomers as desired, provided that it remains capable of carrying out its function as reactive modifier.
- the present invention provides a method for manufacturing mixed resins, as well as a means of making aminoformaldehyde resins of low water content.
- a urea formaldehyde resin may be produced, using a melamine-formaldehyde resin as the reactive solvent, or vice-versa.
- the proportion of the resin used as reactive modifier in the reaction mixture will depend upon the proportion desired, particularly when making a mixed resin, but also will be limited by the extent to which it is capabde of liquifying the reaction system. For instance if the reactive modifier is a liquid resin in which the other reactants are highly soluble it need be used in a proportion lower than would be the case if the other reactants were less soluble in it.
- the molar proportion of the resin used as reactive modifier to the total reactants will not be greater than 40% and will preferably be substantially less.
- the formaldehyde, e.g. paraformaldehyde and the amino compound are generally added to the reactive modifier separately, whilst warming the mixture, to form the reaction mixture in the desired liquid phase.
- ThepH of the system during this stage is alkaline.
- the final condensation may be accelerated by acidifying the reaction mixture if this is.desirable, but in many cases, particularly when melamine is the amino compound, there is no need to accelerate the reaction in this way. If the reaction mixture is acidified, the final product is subsequently neutralized or made alkaline before storage.
- urea/formaldehyde resin to be foamed low molecular weight, partly reacted melamine/formaldehyde resin which improves the film- forming properties of the resin produced.
- the invention may be used in conjunction with the method for manufacturing an aminoformaldehyde resin described in our co-pending UK Patent Application No. 21751/77.
- This example illustrates the preparation of a resin from urea, paraformaldehyde and urea-formaldehyde resin.
- This formulation gives a theoretical solids content of 93.0% and an overall urea:formaldehyde molar ratio of 1:1.33.
- the preparation of the resin was carried out in a 5 litre split reactor fitted with a stainless steel agitator, a thermometer pocket a reflux condenser and a heating mantle.
- the procedure followed in preparing the resin is expressed below in tabular form in Table II.
- the resin was soluble in water, yielding a cloudy solution.
- This example illustrates the preparation of a resin from urea, paraformaldehyde, urea-formaldehyde resin and melamine formaldehyde resin.
- the melamine-formaldehyde resin, paraformaldehyde and urea are dissolved in turn in the U.F. resin under alkaline conditions and then allowed to react under acid conditions.
- the U.F. resin was charged to a reaction vessel provided with a heating/cooling jacket and fitted with a stirrer, thermometer and reflux condenser.
- the pH of the resin was adjusted to 10 with 40% NaOH and heating and stirring commenced.
- a hazy resin solution was obtained having a viscosity of 13,360 poise at 241 ⁇ 2°C and a low water content.
- This example illustrates the use of an aqueous solution of a melamine-formaldehyde resin as reactive modifier in the preparation of a melamine formaldehyde resin.
- This formulation gives a total water content of.17% by weight in the reaction mixture.
- the procedure followed in preparing the resin is expressed in tabular form below in Table V.
- the resin produced had a viscosity of 22, 560 poise at 24°C and an SRY solids content of 77.7%.
- This example illustrates the preparation of a mixed resin using a Uron resin as reactive modifier and urea and paraform as the other reactants.
- the reagents used are detailed in Table VI.
- the bis (methoxymethyl) uron resin is a liquid with a solids content of 95% to 100%.
- the procedure followed was as follows.
- the uron resin was charged to a reaction vessel, stirred and heated.
- the pH of the resin was 8.5.
- the paraform addition was complete after 30 mins, and the mix was maintain at 62 to 64°C for a further 75 mins.
- the paraform was not completely dissolved.
- Urea addition was then begun, maintaining the same temperature and pH, and was completed in 60 mins during which time the solids were dissolving giving a white opaque resin. After a further 28 mins the solids were totally dissolved, the pH was 71 ⁇ 2 and the resin was opaque. Heating was stopped and the liquid resin gradual cleared.
- This example illustrates the preparation of a mixed resin usi a methylated melamine-formaldehyde resin as reactive modifier and urea and paraform as the other reactants.
- BC 309 is a liquid resin commercially available from British Industrial Plastics Limited and has a solids content of 90% (SRY solids content 80%).
- the resin produced was a pasty solid when cold, and had an SRY solids content of 79.8%
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
- This invention relates to the manufacture of resins, and in particular the manufacture of aminoformaldehyde resins,
- Amino-formaldehyde resins are manufactured on a large scale and used in moulding powders, foams for cavity wall insulation etc, for adhesives and in textile finishing. The most commonly used amino compounds are urea and melamine and their derivatives.
- The usual commercial method for the manufacture of aminoformaldehyde resins such as urea-formaldehyde or melamine-formaldehyde resins is to react the amino compound and formaldehyde in an aqueous system at a temperature of 60 to 90°C.
- The product in such cases will inevitably contain a large amount of water which for many uses has to be removed.
- Thus the manufacture of moulding powders from such resins requires a lengthy process in which a large volume of water has to be removed.
- We have also found that in the production of foam from urea-formaldehyde resin, as used, for example, for insulation purposes, foams of superior resilience may be produced from resins of low water content as described in our UK Patent Application No.51269/77.
- It has been disclosed (US Patent No.1,985,937) that polyhydric alcohols can be reacted with methylol ureas, methyl ethers thereof, or dimethyl thiourea to give a clear viscous solution.
- It has been disclosed (US Patent No.1,986,067) that urea can be reacted with a glycol and the product condensed with formaldehyde to give a resinous product. Finally it has been disclosed (UK Patent 1,107,245) that a polyetherurea can be obtained by reacting formaldehyde with glycol to produce a hemiformal, and then reacting the hemiformal with urea or thiourea.
- However, in each of these three prior art disclosures the end product is a material containing a high proportion of glycol which has totally unsatisfactory properties when considered as replacement for modern urea-formaldehyde or melamine-formaldehyde resins.
- It has been proposed (UK Patent No. 1,390,370) to make amino-formaldehyde resins by reaction, in the absence of solvent, of urea or thiourea, paraformaldehyde, and hexamethylene tetramine in a molar ratio in the range from 1:1.1:0.01 to 1:25:0.2. This proposal, however, suffers from the difficulty that in the solid phase, reaction control is virtually impossible and a consistently satisfactory end product is not obtained.
- The present invention is thus concerned with the problem of providing a process for the preparation of amino- formaldehyde resins of lower water content than by the conventional aqueous system, yet avoiding the difficulties of solid phase reaction.
- We propose a solution to this problem in the specification of our co-pending UK Patent Application No 21751/77 in which we describe a method for the manufacture of an amino-formaldehyde resin which comprises reacting an amino compound with formaldehyde or paraformaldehyde at a temperature above 60°C in the liquid phase, the liquid phase being ensured by the presence of a minor proportion of a reactive modifier being a compound capable of taking part in said reaction and also capable of modifying the mixture of reactarts to be liquid at the temperature at which the reaction is to be carried out. Examples are given in that specification of the production of low-water content resins using various different compounds as reactive modifiers. The products so made are useful resins, but the reactive modifiers described are compounds which not only modify the reaction system to the liquid phase at the reaction temperature, but also modify the properties of the resulting resin from those of a simple urea-or melamine-formaldehyde resin.
- The present invention has as its primary objective the preparation of amino-formaldehyde resin of lower water content than those obtained by the conventional aqueous system, whilst avoiding the need to use compounds which will modify the properties of the resin produced.
- According to the present invention a method for the manufacture of an aminoformaldehyde resin comprises reacting an amino compound with formaldehyde or paraformaldehyd in the liquid phase characterized in that said compounds are reacted in the presence of a reactive modifier to ensure said liquid phase, said modifier comprising an aminoformaldehyde resin capable of reaction with further monomers, and which is capable of rendering the mixture of reactants liquid at least at the temperature at which the reaction is to be carried out.
- The reaction is preferably carried out at a temperature above 60°C and more preferably in the range 70 C to 115°C.
- In carrying out the method of this invention water may be omitted, or if added, the amount of water present in the reaction mixture (excluding water formed in the condensation reaction) is preferably less than 6% by weight of the total mixture.
- Although these low water contents in the initial reaction mixture are preferred, low molecular weight liquid resins of low water content are not freely available to use as starting materials at the present time. Thus, we find that a high solids content aqueous solution of a reactant resin (i.e. one capable of reacting with further monomers) can be used successfully as a reactive modifier. The end product when using such a modifier is of lower water content than the products of the usual method of producing such resins. Clearly if desired these products could be used as reactive modifiers in turn, with a correspondingly lower water content in the reaction mixture.
- The reactive modifier, i.e. the initial aminoformaldehyde resin; will, when the reaction is completed, form part of the resin produced. The function of the reactive modifier in the method of this invention is to render the reactant mixture a liquid at the temperature of reaction so that the reaction can be carried out in a liquid phase.
- The aminoformaldehyde resin used as reactive modifier may be a resin containing the same monomers in the same ratio as the resin being manufactured. However, this . need not necessarily be the case and the reactive modifier resin may contain different proportions of monomers, and/or additional or different monomers as desired, provided that it remains capable of carrying out its function as reactive modifier.
- Thus the present invention provides a method for manufacturing mixed resins, as well as a means of making aminoformaldehyde resins of low water content.
- For example, a urea formaldehyde resin may be produced, using a melamine-formaldehyde resin as the reactive solvent, or vice-versa.
- The proportion of the resin used as reactive modifier in the reaction mixture will depend upon the proportion desired, particularly when making a mixed resin, but also will be limited by the extent to which it is capabde of liquifying the reaction system. For instance if the reactive modifier is a liquid resin in which the other reactants are highly soluble it need be used in a proportion lower than would be the case if the other reactants were less soluble in it.
- In general, however the molar proportion of the resin used as reactive modifier to the total reactants will not be greater than 40% and will preferably be substantially less.
- The formaldehyde, e.g. paraformaldehyde and the amino compound are generally added to the reactive modifier separately, whilst warming the mixture, to form the reaction mixture in the desired liquid phase. ThepH of the system during this stage is alkaline. When the three reactants are in the liquid phase the final condensation may be accelerated by acidifying the reaction mixture if this is.desirable, but in many cases, particularly when melamine is the amino compound, there is no need to accelerate the reaction in this way. If the reaction mixture is acidified, the final product is subsequently neutralized or made alkaline before storage.
- Other ingredients may be added to the reaction mixture in the normal manner, a particularly useful ingredient when making a urea/formaldehyde resin to be foamed being low molecular weight, partly reacted melamine/formaldehyde resin which improves the film- forming properties of the resin produced.
- The invention may be used in conjunction with the method for manufacturing an aminoformaldehyde resin described in our co-pending UK Patent Application No. 21751/77.
- ,The invention will now be particularly described by means of the following Examples.
- This example illustrates the preparation of a resin from urea, paraformaldehyde and urea-formaldehyde resin.
-
- This formulation gives a theoretical solids content of 93.0% and an overall urea:formaldehyde molar ratio of 1:1.33.
- The preparation of the resin was carried out in a 5 litre split reactor fitted with a stainless steel agitator, a thermometer pocket a reflux condenser and a heating mantle.
-
- After standing for 8 days an ambient temperature the resin had set to a firm white paste. This could be dispersed in cold water to yield a milky dispersion of pH 9. It was almost completely soluble in boilding water yielding a faintly opalescent solution containing traces of a gelatinous suspension.
- This example illustrates the preparation of a resin from urea, paraformaldehyde, urea-formaldehyde resin and melamine formaldehyde resin.
- In this case the melamine-formaldehyde resin, paraformaldehyde and urea are dissolved in turn in the U.F. resin under alkaline conditions and then allowed to react under acid conditions.
-
- The U.F. resin was charged to a reaction vessel provided with a heating/cooling jacket and fitted with a stirrer, thermometer and reflux condenser. The pH of the resin was adjusted to 10 with 40% NaOH and heating and stirring commenced.
- When the temperature in the vessel had reached 35°C gradual addition of the BL35 M.F. resin was commenced, the total addition taking 15 minutes and the temperature rising to 56°C during that period. The temperature was then increased gradually to 780C when gradual addition of the paraformaldehyde was commenced. During addition of the paraform, which took 55 minutes, the pH was maintained above 8 by addition of 40% NaOH as necessary (2ml NaOH added together) and the temperature was held at 85 to 90°C.
- Gradual addition of urea was then commenced with the heating off, the temperature and pH being held as for the paraform addition, heating and adding 40% NaOH as necessary.
- When the urea addition was complete the pH of the mixture was allowed to fall to 6 and 2 ml of Ammonium Sulphamate added, the reaction being continued over the following 45 minutes. During the reaction the temperature was held in the range 85° to 90°C and the pH in the range 5i to 7 by periodic additions of Ammonium Sulphamate. After the 45 minutes the pH was raised to 8½ by adding 3 ml of NaOH and forced cooling of the reaction vessel was begun.
- A hazy resin solution was obtained having a viscosity of 13,360 poise at 24½°C and a low water content.,
- This example illustrates the use of an aqueous solution of a melamine-formaldehyde resin as reactive modifier in the preparation of a melamine formaldehyde resin.
-
- This formulation gives a total water content of.17% by weight in the reaction mixture.
-
-
- The bis (methoxymethyl) uron resin is a liquid with a solids content of 95% to 100%.
- The procedure followed was as follows. The uron resin was charged to a reaction vessel, stirred and heated. The pH of the resin was 8.5. When the temperature reached 62°C paraform addition was commenced, the temperature being kept in the range 60 to 65°C and the pH at 8.5. The paraform addition was complete after 30 mins, and the mix was maintain at 62 to 64°C for a further 75 mins. The paraform was not completely dissolved. Urea addition was then begun, maintaining the same temperature and pH, and was completed in 60 mins during which time the solids were dissolving giving a white opaque resin. After a further 28 mins the solids were totally dissolved, the pH was 7½ and the resin was opaque. Heating was stopped and the liquid resin gradual cleared.
- When cold the resin slowly became a white paste.
- This example illustrates the preparation of a mixed resin usi a methylated melamine-formaldehyde resin as reactive modifier and urea and paraform as the other reactants.
-
- *BC 309 is a liquid resin commercially available from British Industrial Plastics Limited and has a solids content of 90% (SRY solids content 80%).
-
- The resin produced was a pasty solid when cold, and had an SRY solids content of 79.8%
- It should be noted that the SRY solids content quoted in the above Examples were measured by heating weighed samples of the resins for 3 hours, at 120°C to drive off water of reaction, the residue being regarded as the solids content of the resin. These values should therefore not be confused with the frequently quoted value of resin solids in aqueous solution, in which the non-aqueous content is all taken to be solids, and therefore is generally a very much higher percentage figure.
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB24458/77A GB1603088A (en) | 1977-06-11 | 1977-06-11 | Resin manufacture |
GB2445877 | 1977-06-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000096A1 true EP0000096A1 (en) | 1978-12-20 |
EP0000096B1 EP0000096B1 (en) | 1982-09-01 |
Family
ID=10212030
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78300026A Expired EP0000096B1 (en) | 1977-06-11 | 1978-06-08 | Method for the manufacture of amino-formaldehyde resins |
Country Status (11)
Country | Link |
---|---|
US (1) | US4224423A (en) |
EP (1) | EP0000096B1 (en) |
JP (1) | JPS544987A (en) |
CA (1) | CA1142683A (en) |
DE (1) | DE2862011D1 (en) |
ES (1) | ES470680A1 (en) |
GB (1) | GB1603088A (en) |
IT (1) | IT1156815B (en) |
MX (1) | MX147709A (en) |
YU (1) | YU137278A (en) |
ZA (1) | ZA783136B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3208728A1 (en) * | 1982-03-11 | 1983-09-22 | Cassella Ag, 6000 Frankfurt | CARRIER MATERIALS COATED WITH AMINO PLASTIC DISPERSIONS AND THEIR PROCESSING OF LAYER MATERIALS |
US4499200A (en) * | 1982-05-17 | 1985-02-12 | Chem-Nuclear Systems, Inc. | Compound catalyst system usable for the polymerization or curing of urea-formaldehyde polymeric condensation systems |
US4429075A (en) | 1982-05-17 | 1984-01-31 | Chem-Nuclear Systems, Inc. | Cross-linked urea-formaldehyde polymer matrix compositions containing cyclic intermediate structures |
GB2172894B (en) * | 1985-03-29 | 1989-05-10 | Muirhead Data Communications L | Melamine/formaldehyde and urea/formaldehyde resinous materials |
DE3810114A1 (en) * | 1988-03-25 | 1989-10-12 | Sueddeutsche Kalkstickstoff | METHOD FOR PRODUCING CONDENSATION PRODUCTS CONTAINING SULPHONIC ACID GROUPS WITH A LOW FREE FORMALDEHYDE CONTENT |
US5110898A (en) * | 1988-11-28 | 1992-05-05 | Georgia-Pacific Corporation | Method for manufacturing amino-aldehyde compositions |
US4960856A (en) * | 1988-11-28 | 1990-10-02 | Georgia-Pacific Corporation | Urea-formaldehyde compositions and method of manufacture |
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US2329172A (en) * | 1933-04-03 | 1943-09-07 | Smidth Leonard | Process for making urea-formaldehyde molding compositions and products therefrom |
US3308098A (en) * | 1960-08-30 | 1967-03-07 | American Cyanamid Co | Urea-thiourea formaldehyde resins |
FR1484507A (en) * | 1965-06-24 | 1967-06-09 | Montedison Spa | Process for the preparation of a modified aminotriazine resin and mixtures thereof suitable for the production of laminates which can be molded under low pressure and subsequently shaped |
FR2062186A5 (en) * | 1969-09-18 | 1971-06-25 | Stamicarbon | |
GB1317774A (en) * | 1970-06-02 | 1973-05-23 | British Industrial Plastics | Melamine formaldehyde condensation products |
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US2898324A (en) * | 1956-04-02 | 1959-08-04 | Catalin Corp Of America | Industrial adhesive bonding agent comprising liquid melamine modified urea formaldehyde resin |
BE786056A (en) * | 1971-07-16 | 1973-01-10 | Basf Ag | PROCESS FOR PREPARING STABLE UREE-FORMOL IMPREGNATION RESINS |
US3979341A (en) * | 1974-05-28 | 1976-09-07 | Borden Products Limited | Urea formaldehyde foam |
US4035328A (en) * | 1975-07-03 | 1977-07-12 | Westvaco Corporation | Continuous process for making urea formaldehyde pigment |
US3994850A (en) * | 1976-01-05 | 1976-11-30 | Champion International Corporation | Modified urea-formaldehyde resin adhesive |
US4092277A (en) * | 1977-01-21 | 1978-05-30 | Waverly Chemical Co. | Method for producing chemically stable urea-formaldehyde foams |
-
1977
- 1977-06-11 GB GB24458/77A patent/GB1603088A/en not_active Expired
-
1978
- 1978-06-01 ZA ZA00783136A patent/ZA783136B/en unknown
- 1978-06-02 CA CA000304667A patent/CA1142683A/en not_active Expired
- 1978-06-02 US US05/911,870 patent/US4224423A/en not_active Expired - Lifetime
- 1978-06-07 MX MX173721A patent/MX147709A/en unknown
- 1978-06-08 DE DE7878300026T patent/DE2862011D1/en not_active Expired
- 1978-06-08 EP EP78300026A patent/EP0000096B1/en not_active Expired
- 1978-06-08 YU YU01372/78A patent/YU137278A/en unknown
- 1978-06-09 ES ES470680A patent/ES470680A1/en not_active Expired
- 1978-06-09 IT IT49800/78A patent/IT1156815B/en active
- 1978-06-12 JP JP7068978A patent/JPS544987A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2329172A (en) * | 1933-04-03 | 1943-09-07 | Smidth Leonard | Process for making urea-formaldehyde molding compositions and products therefrom |
US3308098A (en) * | 1960-08-30 | 1967-03-07 | American Cyanamid Co | Urea-thiourea formaldehyde resins |
FR1484507A (en) * | 1965-06-24 | 1967-06-09 | Montedison Spa | Process for the preparation of a modified aminotriazine resin and mixtures thereof suitable for the production of laminates which can be molded under low pressure and subsequently shaped |
FR2062186A5 (en) * | 1969-09-18 | 1971-06-25 | Stamicarbon | |
GB1317774A (en) * | 1970-06-02 | 1973-05-23 | British Industrial Plastics | Melamine formaldehyde condensation products |
Also Published As
Publication number | Publication date |
---|---|
CA1142683A (en) | 1983-03-08 |
ES470680A1 (en) | 1979-02-01 |
IT1156815B (en) | 1987-02-04 |
JPS544987A (en) | 1979-01-16 |
MX147709A (en) | 1983-01-06 |
IT7849800A0 (en) | 1978-06-09 |
GB1603088A (en) | 1981-11-18 |
ZA783136B (en) | 1979-05-30 |
US4224423A (en) | 1980-09-23 |
DE2862011D1 (en) | 1982-10-28 |
EP0000096B1 (en) | 1982-09-01 |
YU137278A (en) | 1982-06-30 |
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