WO1989000587A1 - Process for the preparation of urea-formaldehyde resins - Google Patents
Process for the preparation of urea-formaldehyde resins Download PDFInfo
- Publication number
- WO1989000587A1 WO1989000587A1 PCT/EP1987/000392 EP8700392W WO8900587A1 WO 1989000587 A1 WO1989000587 A1 WO 1989000587A1 EP 8700392 W EP8700392 W EP 8700392W WO 8900587 A1 WO8900587 A1 WO 8900587A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- urea
- mixture
- formaldehyde
- process according
- molar ratio
- Prior art date
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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
- 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
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
Definitions
- This invention relates to a new process for the preparation of urea-formaldehyde resins having a low extractable formaldehyde content.
- Urea-formaldehyde resins are widely used in industry as binders for the production of wood-based materials, particularly chipboard, plywood, and various fibreboards. They are usually employed as colloidal aqueous solutions having a 60-70? ⁇ solids content, the solids content being the percentage weight left when a 2 g sample of the resin is heated at atmospheric pressure at 120°C for 3 hours.
- the resins themselves are complex mixtures of various condensation products, ranging from simple methylolated ureas to fairly high molecular weight materials, and the precise properties of any particular resin will depend upon its molar ratio (i.e. the ratio of formaldehyde to urea when used in its manufacture), the type and proportion of the various linkages within the resin structure, and the proportions of high and low molecular weight material. These last two factors are dependent upon the precise manufacturing method that is used.
- the conventional method of manufacturing urea-formaldehyde resins comprises precondensing urea with formaldehyde in aqueous solution at the reflux at pH 7-9, and heating the mxiture at pH 5-6 until the desired degree of water insolubility or viscosity is reached. The product is neutralised and may then be evaporated and blended with a further quantity of urea if desired.
- Such conventional resins usually have a F:U molar ratio within the range 1.3-2.3:1.
- Resins having a F:U molar ratio as low as 1:1 have been described in British Patent Specification No. 1 420 017. These resins are said to be suitable for binding wood-based materials and are prepared by
- urea-formaldehyde resins having a low content of total extractable formaldehyde and which are suitable for bonding wood-based products, such as fibreboard or particleboard may be prepared with a minimal risk of forming intractable gels if the urea is first methylolated under alkaline conditions at elevated temperature and in a F:U molar ratio within the range 2:1 to 3:1, this mixture is then acidified to a low pH and condensation allowed to continue at elevated temperature. The mixture is neutralised and, in either order, it is concentrated if necessary and urea is added to adjust the F:U molar ratio to within the range 1.8 or less:1.
- This process facilitates formation of a resin which is water soluble and which, when freshly prepared, is completely transparent in appearance. This transparency is lost gradually on storing, the resin becoming slowly opalescent, so that examination of the turbidity of the resin gives an immediate indication of its age or storage conditions.
- this invention provides a process for the preparation of urea-formaldehyde resins which comprises
- the urea-formaldehyde resin should have a solids content of 40 to 75? ⁇ . If it is necessary to evaporate the mixture in order to achieve such a solids content, the evaporation may be carried out, under reduced pressure, either between stages (v) and (vi) or after stage (vi).
- the initial mixing of formaldehyde solution usually containing 35-40? ⁇ by weight of formaldehyde, and urea usually takes place at a F:U molar ratio within the range 2.2 to 2.8:1, especially 2.3 to 2.5:1, and at pH 7-9.
- This mixture is then heated to at least 50°C, usually to at least 80°C and preferably to reflux.
- An acid is then added to bring the pH of the mixture to below 3.5, generally not above 3 and preferably within the range 1-2.5.
- the acid is preferably added while maintaining gentle reflux to keep the exothermic reaction under control.
- the type of acid used is not critical - inorganic or organic acids have both been found to be suitable. Typical acids that may be used include trichloroacetic, toluene-p-sulphonic, hydrochloric, sulphuric, sulphamic and phosphoric acids.
- Heating of the acid mixture in step (iv) is preferably effected at reflux temperature; this heating is usually carried out for a period of from 1 minute to 2 hours, especially from 15 minutes to 1 hour.
- the temeprature of the reaction mxiture may be allowed to fall slightly, but this increases the risk of intractable gel formation, particularly when a formaldehyde:urea ratio up to 2.6:1 is used.
- the temperature below which the reaction mixture should not be allowed to fall depends on the formaldehyde:urea ratio employed, lower ratios requiring higher temperatures to be maintained.
- the reaction mixture is preferably maintained under reflux until the acid condensation stage (iv) has been terminated by the addition of the base in step (v).
- Heating of the reaction mixture in steps (ii), (iv) and (v) may be carried out under pressure, in which case the reflux temperature is, of course, higher and the respective heating time can generally be reduced.
- the base which is used in step (v) is usually sodium hydroxide or potassium hydroxide, but any base that will raise the pH of the mixture to within the range 6.5 to 9 is satisfactory.
- the mixture When the desired pH has been reached, the mixture is usually partially evaporated under reduced pressure to eliminate some of the water present, although this evaporation may take place after the further addition of urea. Evaporation is usually effected below 50°C and preferably within the range 35-45°C.
- the solids content of the product from this evaporation may be varied within fairly wide limits, depending upon the ultimate use of the final resin, but is usually within the range 50-65? ⁇ by weight if the evaporation precedes urea addition, and 60-70? ⁇ by weight if it follows urea addition.
- the mixture When the desired solids content has been reached, the mixture is usually cooled to a temperature below 50°C, preferably to within the range 25-45°C, before urea is added in step (vi). The mixture is.usually stirred for 15 to 60 minutes following addition of urea. Addition of urea gives the desired
- F:U molar ratio preferably from 1.0 to 1.7:1, especially 1.2 to 1.5:1.
- the process of the invention may be carried out batchwise or continuously. Resins made by this new process have their formaldehyde firmly bonded into the molecule, so that both the uncured and cured resins give low values for available formaldehyde. This may be shown by measuring the total free formaldehyde from the uncured resin, the liberated formaldehyde from the hot curing of fibreboard or particle board, and the total extractable formaldehyde from cured fibreboard or particle board.
- resins having remarkably good washdown properties can be prepared, so that apparatus which has been used for the uncured resin may be cleaned easily with a jet of cold water, as can any spillages. This is an important consideration in an industry where large quantities of resin are handled and, if the resin residues are allowed to remain and harden, an expensive strip-down of equipment is needed for cleaning.
- the present invention also facilitates the production of resins having remarkable clarity when freshly prepared.
- Resins having F:U molar ratios of 1.8 or less have always been opalescent, or more usually thick white liquids.
- transparen liquids allows an instant visible means of checking that the resin made by this process has been supplied and that contamination by other materials has not taken place.
- Resins made by the process of this invention are particularly useful in the production of products known as medium density fibreboards, facilitating good processability and high production rates and showing good resistance to premature cure in blending operations.
- These resins may be cured by any conventional means, usually by heating or by the addition of an acid hardener which cures the resins at ambient temperatures, such as formic, phosphoric, or hydrochloric acid, or using a heat-activated hardener such as an acid salt that liberates an acid when heated, preferably ammonium chloride.
- an acid hardener which cures the resins at ambient temperatures, such as formic, phosphoric, or hydrochloric acid
- a heat-activated hardener such as an acid salt that liberates an acid when heated, preferably ammonium chloride.
- Resins prepared by the process of the invention are useful in bonded lignocellulosic material, especially fibreboard or particleboard, the bonded material comprising the resin in cured form as a binder.
- a process for bonding two lignocellulosic surfaces together comprises applying to at least one of the surfaces a urea-formaldehyde resin prepared by the process of the invention, and holding the surfaces together while curing the resin.
- fibreboard or particle board is produced by mixing lignocellulosic fibres or particles, preferably of wood, together with a binder comprising a urea- formaldehyde resin prepared by the process of the invention and, optionally, a heat-activated hardener therefor and heating the resulting mixture under pressure until the binder is cured.
- the optional heat-activated hardener can be any conventional heat- activated hardener for urea-formaldehyde resins, such as an acid salt which liberates an acid on heating, preferably ammonium chloride.
- no hardener is used in the production of fibreboard, while the hardener is used in the manufacture of particleboard.
- the fibreboard or particleboard can be formed in a conventional press, using conventional curing conditions.
- Conventional additives, such as a wax emulsion to improve moisture resistance of the product can be included in the mixture of lignocellulosic material and binder.
- step (v) The process of the invention as hereinbefore defined may be modified to produce resins in a solid particulate form.
- step (v) instead of adding urea to give a resin having a formaldehyde:urea molar ratio of 0.8:1 to 1.8:1, the mixture from step (v), preferably after evaporation as hereinbefore described, is reacted with urea under acid conditions to give a higher molecular weight resin which is then neutralised and dehydrated to give a solid, particulate resin.
- the invention also provides a modification of the process as hereinbefore described which comprises
- step (b) reacting the mixture from step (v) with urea at a pH below 7 to increase the viscosity thereof,
- the reaction of the mixture from step (v) with urea is usually carried out at a pH of 3 to 5 and a temperature of 30 to 60 ⁇ C, using urea in an amount sufficient to give the reaction mixture a formaldehyde:urea molar ratio of from 1.3:1 to 1.9:1, until the viscosity of the reaction mixture is 2 to 4 times the initial viscosity of the mixture.
- this reaction is carried out at a pH of 3.5 to 4.5 and a temperature of 35 to 50°C, using urea in an amount sufficient to give the reaction mixture a formaldehyde:urea molar ratio of 1.5:1 to 1.7:1, until the viscosity of the reaction mixture is 2.5 to 3.5 times the initial viscosity of the mixture.
- the mixture from step (v) is evaporated to a solids content of 40-65? ⁇ , preferably 50-60? ⁇ , by weight, for example by a method as hereinbefore described, before reaction with the urea.
- Acids suitable for use in reducing the pH of the mixture from step (v) include those hereinbefore mentioned as suitable for use in step (iii). Any base that will raise the pH of the mixture to within the range 6.5 to 9 can be used in step (c); for reasons of economy, sodium hydroxide and potassium hydroxide are preferred.
- the dehydration step (d) can be carried out in a conventional spray drier to form the particulate resin.
- particulate resins having low values for available formaldehyde, both in the uncured and cured state can be obtained, these resins having excellent tack properties and being particularly suitable for use in binders for particle board, wafer board and plywood.
- the particulate resin may be mixed with a solid hardener therefor and optionally with additives, e.g. fillers such as wood flour and china clay, to give a storage-stable composition known as a "one-shot" composition which can be activated by the addition of water.
- additives e.g. fillers such as wood flour and china clay
- Suitable solid hardeners for use in such "one-shot" compositions are well-known; aluminium sulphate is the most generally used material.
- the particulate resin may be dissolved or dispersed in water to reform, in effect, a liquid resin which can be mixed with a hardener therefor and optionally with additives for use as a binder.
- Conventional hardeners such as the acid " and salt hardeners hereinbefore mentioned, can be used.
- Aqueous formaldehyde solution (23.93 kg; 38.56? ⁇ HCHO) is treated with sodium hydroxide solution (76.4 ml; 10? ⁇ w/v NaOH), and urea (7.69 kg).
- the mixture which is of pH 9 and has a F:U molar ratio of 2.40:1, is stirred and heated to reflux. It is allowed to cool slightly, to 98°C, and an aqueous solution of sulphamic acid (343.6 ml; 20? ⁇ NH-SO- j H) is added.
- the resultant mixture is of pH 2.0, and this is heated under reflux for 30 minutes.
- sodium hydroxide solution (509.8 ml; 10? ⁇ w/v NaOH) is added to give a neutral solution (pH 7). This is allowed to cool to about 40°C, at which temperature a vacuum is applied and water is distilled from the mixture, a total of 11.3 kg water being collected. The solids content of the mixture is 59? ⁇ . Finally a further quantity of urea is added (5.40 kg), giving a F:U molar ratio of 1.41:1.
- This resin is a water-soluble, colourless transparent liquid having the following properties:
- Aqueous formaldehyde solution (75.68 g; 38.56? ⁇ HCHO) is treated with sodium hydroxide solution (0.24 ml; 10? ⁇ w/v NaOH) followed by urea (24.32 g).
- the mixture which is of pH 9 and has a F:U molar ratio of 2.40:1, is stirred and heated to reflux.
- Phosphoric acid solution (5.0 ml; 20? H,P0.) is added, to bring the mixture to pH 2.0, and it is then heated under reflux for 30 minutes.
- Neutralisation with sodium hydroxide solution (20? ⁇ ) follows and the mixture is evaporated at about 40°C to a solids content of 60? ⁇ .
- the mixture is cooled and urea (17.08 g) is added, giving a F:U molar ratio of 1.41:1.
- This resin is a water-soluble, colourless transparent liquid having the following properties:
- EXAMPLE 3 Softwood core chips (1540 g), dried to a moisture content of 2? ⁇ , are blended with a mixture comprising the resin described in Example 1 (173.8 g), ammonium chloride solution (12.0 g; 10° ⁇ NH.C1), a commercial wax emulsion (12.0 g; 65? ⁇ wax), and water (65.0 g). Part of the resultant blend (1650 g) is placed within a wooden frame 355mm square, and consolidated at room temperature under a pressure of 791 kPa. The resultant consolidated sheet is removed from the frame and compressed at 145°C for 8 minutes under a pressure of 2.77 MPa. The resultant chipboard has a thickness of 19mm. The board is tested, with the following results:
- Aqueous formaldehyde solution (75.68 g; 38.56? ⁇ HCHO) is treated with sodium hydroxide solution (0.24 ml; 10? ⁇ w/v NaOH) and urea (24.32 g).
- This mixture which is of pH 9 and has a F:U ratio of 2.40:1, is heated to reflux and sulphamic acid (1.2 ml; 15? ⁇ NH-SO ⁇ H) is added, giving the mixture a pH of 2.0.
- the mixture is then heated under reflux for 30 minutes after which, while the reflux is maintained, aqueous NaOH is added to pH 7.
- urea (17.08 g) is added, and the product evaporated in vacuo below 40°C to a final weight of 81.12 g.
- the product is a colourless, transparent resin having an F:U molar ratio of 1.41:1, a solids content of 68.5? ⁇ , and a viscosity at 25°C of 0.58 Pa s.
- Aqueous formaldehyde solution (748.3 g; 38.68? ⁇ HCHO) is treated with sodium hydroxide solution (1.2 ml; 20? ⁇ w/v NaOH) and urea (251.7 g).
- the mixture which is of pH 9 and has a F:U molar ratio of 2.30:1, is stirred and heated to reflux.
- Aqueous sulphuric acid (20 ml; 15? ⁇ H principalS0. ) is added, to bring the mixture to pH 2.0, and it is then heated under reflux for 30 minutes.
- Aqueous sodium hydroxide 14 ml; 20% w/v NaOH is added while maintaining the reflux to bring the mixture to pH 7.4.
- Example 1 is repeated to the stage at which water is distilled from the mixture, to a solids content of 57? ⁇ .
- 25.55 parts by weight of urea is added to give a resin having a F:U molar ratio of 1.25:1.
- This resin is a water-soluble colourless transparent liquid having a solids content of 66% and a viscosity at 25°C of 0.32 Pa s.
- EXAMPLE 7 Softwood core chips (1540 g), dried to a moisture content of 2%, are blended with a mixture comprising the resin described in Example 6 (172 g), ammonium chloride solution (12 g; 10? ⁇ NH.Cl), a commercial wax emulsion (12 g: 65% wax), and water (65 g). Part of the resultant blend (1650 g) is placed within a wooden frame 355 mm square, and consolidated at room temperature under a pressure of 791 kPa. The resultant consolidated sheet is removed from the frame and compressed at 145°C for 8 minutes under a pressure of 2.77 MPa. The resultant chipboard (particle board) has a thickness of 19mm. The board is tested, with the following results: F:U molar ratio 1.25:1
- Example 5 is repeated to the stage where the mixture is evaporated, the evaporation being carried out to give a solids content of 50? ⁇ instead of 59? ⁇ .
- the evaporated mixture has a viscosity at 25°C of 0.08 Pa s.
- Urea (30 parts) is added to the evaporated mixture (200 parts) and the resulting mixture is stirred until the urea is dissolved, giving a mixture with a viscosity at 25°C of 0.07 Pa s.
- the F:U molar ratio of the mixture is 1.57:1.
- the temperature of the mixture is adjusted, if necessary, to 34-40°C and aqueous sulphuric acid (1 part; 15? ⁇ H PaulS0. ) is added to bring the mixture to pH 3.9.
- the mixture is stirred for 30 minutes, the temperature rising to 50°C, samples being taken at regular intervals for viscosity determination, until the viscosity of the mixture is increased to 0.22 Pa s.
- Aqueous sodium hydroxide (0.4 part; 20% NaOH) is added to bring the mixture to pH 7.
- the mixture is then dehydrated in a spray -drier to give a resin powder having a softening point of 133°C, a F:U molar ratio of 1.56:1 and a free formaldehyde content of 0.27? ⁇ .
- Aqueous formaldehyde solution (757.1 g; 38.50? ⁇ HCHO) is treated with sodium hydroxide solution (2.4 ml; 10? ⁇ NaOH) and urea (242.9 g).
- the mixture which is of pH 9 and has a F:U molar ratio of 2.4:1, is stirred and heated to 80°C, at which temperature it is maintained for 15 minutes.
- Aqueous sulphuric acid (13.2 ml; 15? ⁇ H virginS0, ) is added, to bring the mixture to pH below 3.5.
- the mixture is cooled to 80°C and heated at this temperature for 30 minutes.
- Aqueous sodium hydroxide (10? ⁇ NaOH) is then added to bring the mixture to pH 7.
- Aqueous formaldehyde solution (784.6 g; 38.5? ⁇ HCHO) is treated with sodium hydroxide solution (2.4 ml; 10? ⁇ NaOH), and urea (215.6 g).
- the mixture which is of pH 9 and has a F:U molar ratio of 2.8:1, is stirred and heated to reflux temperature, where it is maintained for ' 15 minutes.
- An aqueous solution of sulphuric acid (6.6 ml; 15? ⁇ H virginS0.) is added.
- the resulting mixture which is of pH 2.7, is heated under reflux for 30 minutes.
- aqueous sodium hydroxide solution (10? ⁇ NaOH) is added to give a neutral solution (pH 7).
- This solution is evaporated in vacuo at 40°C to a solids content of 59? ⁇ , urea is added to give a F:U molar ratio of 1.25:1, and the mixture is stirred for 60 minutes.
- This resin is a water-soluble, colourless transparent liquid having a solids content of 65% and a viscosity at 25 Q C of 0.1 Pa s.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19873791021 DE3791021T1 (en) | 1987-07-18 | 1987-07-18 | METHOD FOR PRODUCING UREA FORMALDEHYDE RESINS |
NL8720365A NL8720365A (en) | 1986-06-27 | 1987-07-18 | PROCESS FOR THE PREPARATION OF UREA-FORMALDEHYD RESINS. |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8615805A GB2192005B (en) | 1986-06-27 | 1986-06-27 | Process for the preparation of urea-formaldehyde resins |
AT0905487A AT397965B (en) | 1986-06-27 | 1987-07-18 | METHOD FOR PRODUCING UREA FORMALDEHYDE RESINS, METHOD FOR PRODUCING A BINDING AGENT, METHOD FOR PRODUCING A BONDED LIGNOCELLULOSE MATERIAL, AND USES |
CA000542465A CA1290091C (en) | 1986-06-27 | 1987-07-20 | Process for the preparation of urea-formaldehyde resins |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1989000587A1 true WO1989000587A1 (en) | 1989-01-26 |
Family
ID=27151072
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1987/000392 WO1989000587A1 (en) | 1986-06-27 | 1987-07-18 | Process for the preparation of urea-formaldehyde resins |
Country Status (11)
Country | Link |
---|---|
US (1) | US4968772A (en) |
JP (1) | JPH02500031A (en) |
AT (1) | AT397965B (en) |
AU (1) | AU605504B2 (en) |
BE (1) | BE1000759A4 (en) |
CA (1) | CA1290091C (en) |
FR (1) | FR2618789B1 (en) |
GB (1) | GB2192005B (en) |
NL (1) | NL8720365A (en) |
SE (1) | SE462392B (en) |
WO (1) | WO1989000587A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103242201A (en) * | 2013-04-26 | 2013-08-14 | 中科院广州化学有限公司 | Preparation method of urea formaldehyde intermediate dimethylol urea |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8715305D0 (en) * | 1987-06-30 | 1987-08-05 | Ciba Geigy Ag | Process |
FR2625204B1 (en) * | 1987-12-23 | 1991-12-06 | Charbonnages Ste Chimique | NEW PROCESS FOR THE MANUFACTURE OF UREE-FORMOL RESINS |
GB9014985D0 (en) * | 1990-07-06 | 1990-08-29 | Dyno Industrier As | Formaldehyde resin curing agents |
US5243015A (en) * | 1992-06-25 | 1993-09-07 | Georgia-Pacific Resins, Inc. | Latent catalyzed phenolic resole resin composition |
WO1995022133A1 (en) * | 1994-02-08 | 1995-08-17 | Nauchno-Tekhnologicheskoe Predpriyatie 'ligand' | Method of obtaining a carbamide-formaldehyde resin and a condensate for the manufacture of the same |
US6495655B2 (en) * | 1996-09-30 | 2002-12-17 | David H. Blount | Production of amino-aldehyde-phosphate resins and copolymers |
US5854309A (en) * | 1996-09-30 | 1998-12-29 | Blount; David H. | Flame retardant compositions utilizing amino condensation compounds |
US6051086A (en) * | 1998-06-08 | 2000-04-18 | Orica Explosives Technology Pty Ltd. | Buffered emulsion blasting agent |
DE19849380A1 (en) * | 1998-10-27 | 2000-05-04 | Basf Ag | Low-water formroxane formaldehyde solutions |
CN100344720C (en) * | 2006-03-30 | 2007-10-24 | 浙江林学院 | Environment protection, low cost urea resin gel |
US20090163656A1 (en) * | 2007-12-21 | 2009-06-25 | Envont Llc | Hybrid vehicle systems |
WO2012067072A1 (en) * | 2010-11-15 | 2012-05-24 | 日産化学工業株式会社 | Softened thermosetting resin particles |
CN107344992B (en) * | 2017-06-01 | 2020-01-14 | 东莞市贝辉装饰材料有限公司 | Low-formaldehyde urea-formaldehyde resin and preparation method and application thereof |
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FR2166232A1 (en) * | 1971-12-27 | 1973-08-10 | Sir Soc Italiana Resine Spa | |
FR2165995A1 (en) * | 1971-12-27 | 1973-08-10 | Sir Soc Italiana Resine Spa | |
GB1480787A (en) * | 1975-09-11 | 1977-07-27 | Ciba Geigy Ag | Ureaformaldehyde resins |
GB1486342A (en) * | 1974-01-02 | 1977-09-21 | Monsanto Co | Storage stable urea formaldehyde resin syrup and process therefor |
EP0006112A1 (en) * | 1978-06-10 | 1980-01-09 | Ab Casco | Process for preparing thermosetting urea formaldehyde resins and their use for impregnating and/or coating supporting webs of wood-based boards |
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AU4804472A (en) * | 1972-01-27 | 1974-04-26 | Borden Inc | Urea-formaldehyde condensates |
BE795631A (en) * | 1972-02-19 | 1973-08-20 | Basf Ag | AMINOPLAST BINDERS FOR WOOD-BASED MATERIALS |
US3962166A (en) * | 1972-06-05 | 1976-06-08 | United Merchants And Manufacturers, Inc. | Stable urea-formaldehyde compositions |
DE2448472C3 (en) * | 1974-10-11 | 1979-08-30 | Th. Goldschmidt Ag, 4300 Essen | Process for the production of solutions of urea-formaldehyde impregnating resins |
US4032515A (en) * | 1974-11-04 | 1977-06-28 | Koppers Company, Inc. | Curable resorcinol terminated urea-formaldehyde resins |
GB1570339A (en) * | 1976-06-23 | 1980-06-25 | Ici Ltd | Process for producing aqueous-formaldehyde resin solutions |
IT1209203B (en) * | 1980-04-10 | 1989-07-16 | Montedison Spa | UREIC NECKLACE WITH LOW DEVELOPMENT OF FORMALDEHYDE AND HIGH TACK VALUE. |
US4381368A (en) * | 1982-02-16 | 1983-04-26 | Spurlock Harold N | Process for the preparation of urea-formaldehyde resins |
US4410685A (en) * | 1982-09-10 | 1983-10-18 | Borden, Inc. | Hydrolytically stable urea-formaldehyde resins and process for manufacturing them |
GB2150939B (en) * | 1983-12-09 | 1987-02-04 | Enigma Nv | A process for preparing urea-formaldehyde resins |
-
1986
- 1986-06-27 GB GB8615805A patent/GB2192005B/en not_active Expired
-
1987
- 1987-07-18 AT AT0905487A patent/AT397965B/en not_active IP Right Cessation
- 1987-07-18 JP JP62504528A patent/JPH02500031A/en active Pending
- 1987-07-18 WO PCT/EP1987/000392 patent/WO1989000587A1/en active Application Filing
- 1987-07-18 US US07/275,036 patent/US4968772A/en not_active Expired - Fee Related
- 1987-07-18 AU AU77808/87A patent/AU605504B2/en not_active Ceased
- 1987-07-18 NL NL8720365A patent/NL8720365A/en not_active Application Discontinuation
- 1987-07-20 CA CA000542465A patent/CA1290091C/en not_active Expired - Lifetime
- 1987-07-27 BE BE8700827A patent/BE1000759A4/en not_active IP Right Cessation
- 1987-07-30 FR FR878710797A patent/FR2618789B1/en not_active Expired - Lifetime
-
1988
- 1988-10-19 SE SE8803744A patent/SE462392B/en not_active IP Right Cessation
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FR2166232A1 (en) * | 1971-12-27 | 1973-08-10 | Sir Soc Italiana Resine Spa | |
FR2165995A1 (en) * | 1971-12-27 | 1973-08-10 | Sir Soc Italiana Resine Spa | |
GB1486342A (en) * | 1974-01-02 | 1977-09-21 | Monsanto Co | Storage stable urea formaldehyde resin syrup and process therefor |
GB1480787A (en) * | 1975-09-11 | 1977-07-27 | Ciba Geigy Ag | Ureaformaldehyde resins |
EP0006112A1 (en) * | 1978-06-10 | 1980-01-09 | Ab Casco | Process for preparing thermosetting urea formaldehyde resins and their use for impregnating and/or coating supporting webs of wood-based boards |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103242201A (en) * | 2013-04-26 | 2013-08-14 | 中科院广州化学有限公司 | Preparation method of urea formaldehyde intermediate dimethylol urea |
CN103242201B (en) * | 2013-04-26 | 2015-06-10 | 中科院广州化学有限公司 | Preparation method of urea formaldehyde intermediate dimethylol urea |
Also Published As
Publication number | Publication date |
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SE462392B (en) | 1990-06-18 |
ATA905487A (en) | 1993-12-15 |
SE8803744D0 (en) | 1988-10-19 |
FR2618789B1 (en) | 1990-10-12 |
AU605504B2 (en) | 1991-01-17 |
AT397965B (en) | 1994-08-25 |
AU7780887A (en) | 1989-02-13 |
GB2192005A (en) | 1987-12-31 |
CA1290091C (en) | 1991-10-01 |
NL8720365A (en) | 1989-05-01 |
GB2192005B (en) | 1989-12-13 |
US4968772A (en) | 1990-11-06 |
BE1000759A4 (en) | 1989-03-28 |
SE8803744L (en) | 1989-01-19 |
FR2618789A1 (en) | 1989-02-03 |
JPH02500031A (en) | 1990-01-11 |
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