EP0000096B1 - Method for the manufacture of amino-formaldehyde resins - Google Patents
Method for the manufacture of amino-formaldehyde resins Download PDFInfo
- Publication number
- EP0000096B1 EP0000096B1 EP78300026A EP78300026A EP0000096B1 EP 0000096 B1 EP0000096 B1 EP 0000096B1 EP 78300026 A EP78300026 A EP 78300026A EP 78300026 A EP78300026 A EP 78300026A EP 0000096 B1 EP0000096 B1 EP 0000096B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formaldehyde
- resin
- 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.)
- Expired
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- 229920005989 resin Polymers 0.000 title claims description 70
- 239000011347 resin Substances 0.000 title claims description 70
- 238000000034 method Methods 0.000 title claims description 24
- ZHNUHDYFZUAESO-OUBTZVSYSA-N aminoformaldehyde Chemical compound N[13CH]=O ZHNUHDYFZUAESO-OUBTZVSYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 28
- 239000003607 modifier Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229920000877 Melamine resin Polymers 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- -1 amino compound Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- 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
- 230000002378 acidificating effect Effects 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229920002866 paraformaldehyde Polymers 0.000 description 14
- 238000007792 addition Methods 0.000 description 12
- 229930040373 Paraformaldehyde Natural products 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 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 3
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 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
- 238000000465 moulding Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000006260 foam Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- ZNNYSTVISUQHIF-UHFFFAOYSA-N formaldehyde;thiourea Chemical compound O=C.NC(N)=S ZNNYSTVISUQHIF-UHFFFAOYSA-N 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
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 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
- 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
- 239000002904 solvent Substances 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
- 239000000725 suspension Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 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 amino-formaldehyde 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.
- amino-formaldehyde resins such as urea-formaldehyde or melamine-formaldehyde resins
- urea-formaldehyde or melamine-formaldehyde resins The usual commercial method for the manufacture of amino-formaldehyde resins is to react the amino compound and formaldehyde in an aqueous system at a temperature of 60 to 90°C.
- 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, and not requiring the presence of compounds which will modify the properties of the resin.
- a method for the manufacture of an amino-formaldehyde resin comprises reacting in the liquid phase an amino compound, selected from urea and melamine, with formaldehyde in a reaction system including, as reactive modifier, an amino-formaldehyde resin, characterised in that said reactive modifier resin is itself a urea-formaldehyde or melamine-formaldehyde resin which reacts with further amino-compound and/or formaldehyde and is in the form of a liquid resin or an aqueous solution of at least 50% solids content, and renders the mixture of reactants liquid at least at the temperature at which the reaction is to be carried out, the amino-compound and the formaldehyde being introduced into said reactive modifier in a solid form neither dissolved nor dispersed in water.
- 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.
- a preferred reactive modifier is thus a low molecular weight liquid amino-formaldehyde resin having a water content of less than 10% by weight.
- 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
- a reactive modifier i.e. a solution having a solids content of at least 50% by weight.
- 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 amino-formaldehyde 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 amino-formaldehyde 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 resins may contain different proportions of monomers, and/or additional 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 amino-formaldehyde resins of low water content.
- a urea formaldehyde resin may be produced, using a melamine-formaldehyde resin as the reactive modifier 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 capable of liquifying the reactive 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.
- the pH 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.
- reaction mixture is acidified, the final product is subsequently neutralised or made alkaline before storage.
- urea/formaidehyde resin to be foamed low molecular weight, partly reacted melamine/formaldehyde resin which improves the film-forming properties of the resin produced.
- This example illustrates the preparation of a resin from urea, paraformaldehyde and urea-formaldehyde resin.
- the reagent quantities used are detailed in Table 1.
- 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, and thermometer pocket a reflux condenser and a heating mantle.
- the resin was soluble in water, yielding a cloudy solution. After standing for 8 days at 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 boiling 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.
- 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 (1336 PaS) at 24.5°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.
- BL 34 resin is a spray-dried Melamine-Formaldehyde resin of M:F ratio 1:2.0, containing 2% free moisture and an SRY solids content of 93%.
- This formulation gives a total water content of 17% by weight in the reaction mixture.
- the resin produced had a visocisty 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 maintained 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 7.5 and the resin was opaque. Heating was stopped and the liquid resin gradually cleared.
- This example illustrates the preparation of a mixed resin using a methylated melamine- formaldehyde resin as reactive modifier, and urea and paraform as the othe 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)
Description
- This invention relates to the manufacture of resins, and in particular the manufacture of amino-formaldehyde 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 amino-formaldehyde 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.
- It has been proposed (French Patent No. 2,062,186) to make resin solutions of good storage stability by reacting amino compound and formaldehyde in the presence of a highly condensed melamine-formaldehyde resin. However, in this case the reaction system is conventional apart from the presence of the pre-formed resin and the usual 30% formaldehyde solution in water is used.
- In US Patent No. 3,308,098 there is disclosed a stage by stage process for making a high solids syrup containing a urea-formaldehyde condensate and a thiourea-formaldehyde condensate but to achieve the high solids the process described requires a concentration step.
- It has been disclosed (French Patent No. 1,484,507) that an alkanolamine can be reacted with paraformaldehyde in substantially water-free conditions, and the product reacted with a triazine such as melamine to give a resin of low water content.
- Similarly it has been disclosed (UK Patent No. 1,317,774) that formaldehyde can be reacted with aliphatic hydroxylated monoamine as defined in UK Patent No. 1,012,319 and the product condensed with melamine to give a resinous product, the reaction stages being carried out at high solids contents. The formaldehyde can alternatively be reacted first with the melamine and then with the hydroxylated monoamine.
- However, in each of these latter two prior art patent disclosures a major ingredient of the reaction system is an alkanolamine which is a modifier for melamine-formaldehyde resins and simple urea-formaldehyde or melamine-formaldehyde resins cannot be produced using these techniques.
- tt 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, and not requiring the presence of compounds which will modify the properties of the resin.
- According to the present invention a method for the manufacture of an amino-formaldehyde resin comprises reacting in the liquid phase an amino compound, selected from urea and melamine, with formaldehyde in a reaction system including, as reactive modifier, an amino-formaldehyde resin, characterised in that said reactive modifier resin is itself a urea-formaldehyde or melamine-formaldehyde resin which reacts with further amino-compound and/or formaldehyde and is in the form of a liquid resin or an aqueous solution of at least 50% solids content, and renders the mixture of reactants liquid at least at the temperature at which the reaction is to be carried out, the amino-compound and the formaldehyde being introduced into said reactive modifier in a solid form neither dissolved nor dispersed in water.
- 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.
- A preferred reactive modifier is thus a low molecular weight liquid amino-formaldehyde resin having a water content of less than 10% by weight.
- 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 i.e. a solution having a solids content of at least 50% by weight. 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 amino-formaldehyde 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 amino-formaldehyde 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 resins may contain different proportions of monomers, and/or additional 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 amino-formaldehyde resins of low water content.
- For example, a urea formaldehyde resin may be produced, using a melamine-formaldehyde resin as the reactive modifier 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 capable of liquifying the reactive 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. The pH 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 neutralised 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/formaidehyde 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 will now be particularly described by means of the following Examples.
-
- 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, and thermometer pocket a reflux condenser and a heating mantle.
-
- The resin was soluble in water, yielding a cloudy solution. After standing for 8 days at 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 boiling 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 78°C 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 5.5 to 7 by periodic additions of Ammonium Sulphamate. After the 45 minutes the pH was raised to 8.5 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 (1336 PaS) at 24.5°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.
-
- *BL 34 resin is a spray-dried Melamine-Formaldehyde resin of M:F ratio 1:2.0, containing 2% free moisture and an SRY solids content of 93%.
- (lts usual use is in impregnation of print and overlay papers in laminating)
- This formulation gives a total water content of 17% by weight in the reaction mixture.
-
- The resin produced had a visocisty of 22,560 poise at 24°C and an SRY solids content of 77.7%.
-
- 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 maintained 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 7.5 and the resin was opaque. Heating was stopped and the liquid resin gradually cleared.
- When cold the resin slowly became a white paste.
- This example illustrates the preparation of a mixed resin using a methylated melamine- formaldehyde resin as reactive modifier, and urea and paraform as the othe 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 (8)
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 EP0000096A1 (en) | 1978-12-20 |
EP0000096B1 true 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 |
Family Cites Families (11)
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 |
US2898324A (en) * | 1956-04-02 | 1959-08-04 | Catalin Corp Of America | Industrial adhesive bonding agent comprising liquid melamine modified urea formaldehyde resin |
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 |
BE756226A (en) * | 1969-09-18 | 1971-03-16 | Stamicarbon | |
GB1317774A (en) * | 1970-06-02 | 1973-05-23 | British Industrial Plastics | Melamine formaldehyde condensation products |
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
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 |
EP0000096A1 (en) | 1978-12-20 |
YU137278A (en) | 1982-06-30 |
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