US3645841A - Water-soluble quaternized melamine-aldehyde resins and their application in the paper industry - Google Patents
Water-soluble quaternized melamine-aldehyde resins and their application in the paper industry Download PDFInfo
- Publication number
- US3645841A US3645841A US888933A US3645841DA US3645841A US 3645841 A US3645841 A US 3645841A US 888933 A US888933 A US 888933A US 3645841D A US3645841D A US 3645841DA US 3645841 A US3645841 A US 3645841A
- Authority
- US
- United States
- Prior art keywords
- glyoxal
- melamine
- paper
- resin
- formaldehyde
- 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 - Lifetime
Links
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
- C08G12/40—Chemically modified polycondensates
-
- 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
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
Definitions
- ABSTRACT A water-soluble resin is prepared by condensing 1 to 6 moles [52] US. CL ..l62/166, 260/ 17.3 R, 260/67.6, f an aldehyde compound Such as glyoxal with 1 mole f 260/2495 melamine and reacting the resulting product with 0.2 to 0.5 [51] Int. Cl.
- the present invention relates to water-soluble resins, especially intended to impart good strength to paper inthe wet state.
- the invention also relates to a method of preparation of the said resins and also to a method of manufacture of the paper in which they are employed.
- paper is composed of an assembly of cellulose fibers feebly bound to each other, which results in a low strength of this material, especially in the moist state.
- the strength of the paper can be increased by various methods which vary from the improvement of refining to the introduction into the paper of natural or synthetic products which increase the adherence of the fibers to each other.
- Glyoxal is however very soluble in water and does not have any particular affinity for papermaking fibers, so that it is not possible to introduce it into the pulping machine; it is considered sufficient to treat the paper produced in sheet form by glyoxal, which substantially complicates the process of manufacture.
- the object of the present invention is to resolve in a satisfactory manner the general problem of the strength of paper in the wet state.
- the applicants have in fact found that new resins obtained-by the condensation of amino-triazines and more particularly of melamine with glyoxal, or with mixtures of glyoxal and formaldehyde, followed by quaternization of the condensation product obtained, resulted, when they were added to the paper pulp in the pulping machine, in an increased strength of the paper sheet in the wet state, and in the maintenance of this improvement in the strength of the paper during a more or less long immersion which can be regulated at will by varying the composition of the resin, and especially, all other things being equal, by modifying the respective proportions of glyoxal and formaldehyde.
- the resin can be obtained in the form of a powder soluble in water which provides convenience of transport and stability during storage;
- the resin produces a substantial increase in the strength of the paper in the dry state and an increase in strength in the wet state, this strength having a more or less long duration, depending on the composition of the condensation product of the amino-triazine with glyoxal and formaldehyde.
- condensation products of amino-triazine and more particularly of melamine with glyoxal or glyoxal and formaldehyde are prepared under pH conditions in the vicinity of neutrality, and such resins are generally insoluble or only slightly soluble in water; they are converted to water-soluble products by the action of an appropriate quaternization agent.
- the molecular proportions of glyoxal with respect to the melamine may vary from 1 to 6.
- the most condensed and most advantageous products are obtained with a molecular ration of glyoxal to melamine in the vicinity of 4; after quaternization, they give the most viscous solutions.
- the molecular ration is lower than 3, the condensation products are difficult to quatemize, and the resins obtained are generally only slightly soluble in water.
- the molecular ratio is higher than 4, on the other hand, there are obtained condensation products which are soluble in water but which have very low viscosity after quaternization and which therefore are probably only slightly condensed.
- the condensation of melamine with the aldehydes is carried out in an aqueous solution at a pH value varying from 5 to 8, preferably from 5 to 7, without it being necessary to utilize a buffer mixture in order to stabilize the pH value.
- the temperature of the condensation is less then l00 C.
- the products of condensation of melamine and glyoxal or melamine-glyoxalformaldehyde according to the invention are generally insoluble or only slightly soluble in water and have very little or no affinity for cellulose fibers. The purpose of quaternization is to render them soluble and to give them a greater affinity for the fibers.
- condensation products according to the invention cannot be rendered dispersable in water by the addition of hydrochloric acid as is usually done in the case of the melamine-formaldehyde resins applied to the paper industry. There is in fact produced with the resins, according to the invention, an acid hydrolysis which results in a characteristic reduction in the viscosity of the solutions.
- the products of condensation of the amino-triazines and more particularly of melamine with glyoxal or glyoxal and formaldehyde, which possess a basic character are converted to quaternary ammonium salts by the action of a quaternization agent.
- Dimethyl sulphate is generally employed, but any other quaternization agent may generally be employed, such as the alkyl halides or the esters of aryl-sulphonic acid.
- the proportion of dimethyl sulphate may vary from 0.2 to 0.5 mol per molecule of melamine.
- condensation products of melamine and formaldehyde generally give, after quaternization, products which are insoluble in water
- the condensation products, according to the invention are soluble in water,.after quaternization, the presence of glyoxal increasing the solubility of the resins in an unexpected manner.
- the quaternized resins of the invention are obtained in the form of yellowish aqueous solutions having a viscosity variable according to the degree of condensation and the degree of ripening or curing. In fact, this viscosity increases with time, but less rapidly than for the melamine-formaldehyde resins, and the resins according to the invention maintain their solubility in water for several months.
- the quatemized aqueous resin solutions according to the invention may be evaporated at low temperature in order to give powders which are stable at ordinary temperatures and can be employed by simply dissolving in water, which constitutes an advantage with respect to the melamine-formaldehyde resins usually employed in papermaking which, if they are sold ready for use, have a very limited storage life, while if they are sold in the form of trimethylol-melamine in powder, compel the user to prepare his resin himself and to allow it to ripen.
- the resins according to the invention may be introduced into the pulping machine in doses from 1 to percent, preferably from 2 to 4 percent calculated by weight of dry resin with respect to the dry pulp.
- the resin is absorbed by the fiber, which results in a neutralization of the zeta potential of the fiber. It is not necessary to employ additional adhesion products such as rosin or aluminum sulphate.
- results obtained by carrying out the measurements on dry paper are expressed as a percentage of increase in resistance to bursting as compared with the paper which does not contain resin.
- the measurements of resistance to bursting of the wet paper are carried out after 30 seconds and after 30 minutes immersion of the paper in water.
- the wet resistance is expressed as a percentage of the resistance of the same paper treated and dry, as a percentage of the resistance of the sample paper dry, not containing resin, and also with respect to the wet strength of a specimen paper which does not contain resin.
- EXAMPLE 1 50.4 grams of melamine (0.4 mol) are introduced with stirring into 232 grams of an aqueous solution of glyoxal at 40 percent (1.6 mols) and the temperature is brought up to 60 C. The initial pH value is about 5 to 6. After the melamine has dissolved, a gradual thickening of the medium takes place. The mixture is kept at 60C. for 3 hours.
- the resin obtained is of a yellowish fluorescent color, has a viscosity of 250 poises at 25 C. and a pH value of 3.9.
- This resin is incorporated in a bisulphite paper pulp having a degree of refining of 30 SR, and a pH value of 4.5, in a proportion of 2 percent. After shaping a sheet of paper and drying for 5 minutes at 90 C., followed by 30 minutes at 100 C., it is found that the resistance to bursting of the dry paper thus obtained and conditioned is increased by 24 percent as compared with a specimen paper which does not contain the resin according to the invention.
- the resistance to bursting is compared, in the first place with the resistance of the same dry treated paper. It is found that it is 25 percent of the resistance of the dry paper. it is then compared with that of a specimen paper which does not contain the resin; the resistance is 31.3 percent of that of the dry specimen paper and equal to 3.5 times the resistance of the specimen paper also immersed for 30 seconds in water. After 30 minutes immersion, the resistance to bursting is 15.5 percent of the same paper treated dry, 20.2 percent of the resistance of the specimen paper dry, and equal to 2.2 times the resistance of the specimen paper immersed for 30 minutes in water.
- EXAMPLE 2 There are mixed in a water bath at 60 C., in the order given and with stirring, 25.2 grams of melamine (0.2 mol), 86 grams of glyoxal at 40 percent (0.6 mol) and 27.2 grams of formaldehyde in an aqueous solution at 44 percent (0.4 mol).
- the initial dispersion is at a pH value of 4.6; the pH increases gradually to 8 as and when the melamine passes into solution.
- the medium thickens gradually in a period of 2 hours.
- the resin obtained is a gel soluble in its water of formation, insoluble by dilution or cooling.
- the preparation is continued by quatemizing the resin in the following manner: 12.6 grams of dimethyl sulphate (0.1 mol) are introduced in 30 minutes at 60-65 C., after which the stirring is still continued for 30 minutes. The viscosity diminishes during the introduction of the dimethyl sulphate and then increases. The final concentration is brought to 50 percent by diluting with 17.4 grams of water.
- the resin obtained is a viscous fluorescent yellow syrup which has a viscosity after 24 hours of 50 poises at 25 C. and a pH value of 4.7.
- the viscosity increases up to 20,000 poises after several months, the resin remaining however perfectly soluble in water.
- the 10 percent aqueous solutions are stable for several weeks at 20 C. By evaporating 50 percent solutions there are obtained powders which are stable and soluble in the cold state.
- EXAMPLE 3 There are mixed with stirring at 60-65 C. and in the order given, 25.2 grams of melamine (0.2 mol), 86 grams of glyoxal at 40 percent (0.6 mol) and 41 grams of formaldehyde in solution at 44 percent (0.6 mol).
- the medium thickens rapidly in 3 hours.
- the pale yellow resin is insoluble by dilution in water or by coolmg.
- Quatemization is effected by introducing in 15 minutes at 60-65 C., 12.6 grams of dimethyl sulphate (0.1 mol). There is a partial fluidification of the medium and then a gradual thickening in 30 minutes. The concentration is brought to 50 percent by the addition of 15.6 grams of water.
- This resin becomes completely jellified after one month at 20 C., but remains entirely soluble in water after several months of storage.
- the 10 percent solutions are stable for several weeks at 20 C.
- a water-soluble resin for application in the paper industry consisting essentially of the condensation product of melamine and an aldehyde compound, wherein the molecular ratio of the aldehyde compound to the melamine is between I and 6, reacted with a quatemization agent selected from the group consisting of dimethyl sulfate, alkyl halide and esters of arylsulfonic acids, in the amount of 0.2 to 0.5 moles of said quatemization agent per mole of said melamine.
- said aldehyde compound is selected from the group consisting of glyoxal and a mixture of formaldehyde and glyoxal.
- a method of preparation of resins comprising the condensation product of melamine and an aldehyde compound selected from the group consisting of glyoxal and a mixture of formaldehyde and glyoxal, reacted with a quatemization agent selected from the group of dimethyl sulphate, alkyl halide and esters of arylsulfonic acids, comprising the carrying out of the condensation reaction between said melamine and l to 6 moles of said aldehyde compound per mole of said melamine in an aqueous medium at a pH value between 5 and 8, at a temperature lower than C.
- a method for the manufacture of soft paper having good temporary resistance to humidity comprising providing an aqueous slurry of paper pulp having a neutral or slightly alkaline pH up to about 8;
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR181890 | 1968-12-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3645841A true US3645841A (en) | 1972-02-29 |
Family
ID=8659401
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US888933A Expired - Lifetime US3645841A (en) | 1968-12-30 | 1969-12-29 | Water-soluble quaternized melamine-aldehyde resins and their application in the paper industry |
Country Status (11)
Country | Link |
---|---|
US (1) | US3645841A (tr) |
BE (1) | BE743673A (tr) |
DE (1) | DE1965373C3 (tr) |
DK (1) | DK132089C (tr) |
FI (1) | FI50250C (tr) |
FR (1) | FR1602233A (tr) |
GB (1) | GB1289860A (tr) |
LU (1) | LU60096A1 (tr) |
NL (2) | NL6919597A (tr) |
NO (1) | NO129681B (tr) |
SE (2) | SE365269B (tr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58118814A (ja) * | 1981-12-29 | 1983-07-15 | ソシエテ・フランセ−ズ・ヘキスト | 新規なカチオンアミノプラスチツク樹脂、その製造法およびその水処理への応用 |
US4492643A (en) * | 1981-11-05 | 1985-01-08 | Degussa Aktiengesellschaft | Bismelamine stabilizers |
US5294352A (en) * | 1985-06-27 | 1994-03-15 | Waldmann John J | Compositions for the detackification of paint spray booth water and waste water |
US9447221B2 (en) | 2014-07-03 | 2016-09-20 | Johns Manville | Formaldehyde-free melamine carbohydrate binders for improved fire- resistant fibrous materials |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2424234A1 (fr) * | 1978-04-24 | 1979-11-23 | Hoechst France | Procede de traitement des eaux brutes et des eaux residuaires |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2624686A (en) * | 1948-11-04 | 1953-01-06 | Olin Mathieson | High wet-strength paper and process of making |
GB831297A (en) * | 1957-06-19 | 1960-03-30 | Tootal Broadhurst Lee Co Ltd | Improvements in and relating to the treatment of fabrics |
US3068190A (en) * | 1958-12-05 | 1962-12-11 | Dal Mon Research Co | Condensation of aldehydes with triazinyl aryl sulfonic acid derivatives and process of preparing same |
GB1071307A (en) * | 1965-02-12 | 1967-06-07 | Ciba Ltd | Process for the preparation of finely divided, insoluble and infusible melamine-formaldehyde condensation products |
US3556932A (en) * | 1965-07-12 | 1971-01-19 | American Cyanamid Co | Water-soluble,ionic,glyoxylated,vinylamide,wet-strength resin and paper made therewith |
-
0
- NL NL137596D patent/NL137596C/xx active
-
1968
- 1968-12-30 FR FR181890A patent/FR1602233A/fr not_active Expired
-
1969
- 1969-12-22 SE SE17698/69A patent/SE365269B/xx unknown
- 1969-12-22 SE SE7212311A patent/SE377477B/xx unknown
- 1969-12-24 NO NO05127/69A patent/NO129681B/no unknown
- 1969-12-24 BE BE743673D patent/BE743673A/xx not_active IP Right Cessation
- 1969-12-24 LU LU60096D patent/LU60096A1/xx unknown
- 1969-12-29 FI FI693753A patent/FI50250C/fi active
- 1969-12-29 US US888933A patent/US3645841A/en not_active Expired - Lifetime
- 1969-12-29 DK DK687469A patent/DK132089C/da active
- 1969-12-30 GB GB1289860D patent/GB1289860A/en not_active Expired
- 1969-12-30 NL NL6919597A patent/NL6919597A/xx unknown
- 1969-12-30 DE DE1965373A patent/DE1965373C3/de not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2624686A (en) * | 1948-11-04 | 1953-01-06 | Olin Mathieson | High wet-strength paper and process of making |
GB831297A (en) * | 1957-06-19 | 1960-03-30 | Tootal Broadhurst Lee Co Ltd | Improvements in and relating to the treatment of fabrics |
US3068190A (en) * | 1958-12-05 | 1962-12-11 | Dal Mon Research Co | Condensation of aldehydes with triazinyl aryl sulfonic acid derivatives and process of preparing same |
GB1071307A (en) * | 1965-02-12 | 1967-06-07 | Ciba Ltd | Process for the preparation of finely divided, insoluble and infusible melamine-formaldehyde condensation products |
US3556932A (en) * | 1965-07-12 | 1971-01-19 | American Cyanamid Co | Water-soluble,ionic,glyoxylated,vinylamide,wet-strength resin and paper made therewith |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4492643A (en) * | 1981-11-05 | 1985-01-08 | Degussa Aktiengesellschaft | Bismelamine stabilizers |
JPS58118814A (ja) * | 1981-12-29 | 1983-07-15 | ソシエテ・フランセ−ズ・ヘキスト | 新規なカチオンアミノプラスチツク樹脂、その製造法およびその水処理への応用 |
US4481116A (en) * | 1981-12-29 | 1984-11-06 | Societe Francaise Hoechst | Cationic aminoplastic resin, preparation process and application thereof to water treatment |
JPH0242093B2 (tr) * | 1981-12-29 | 1990-09-20 | ||
US5294352A (en) * | 1985-06-27 | 1994-03-15 | Waldmann John J | Compositions for the detackification of paint spray booth water and waste water |
US9447221B2 (en) | 2014-07-03 | 2016-09-20 | Johns Manville | Formaldehyde-free melamine carbohydrate binders for improved fire- resistant fibrous materials |
US9611350B2 (en) | 2014-07-03 | 2017-04-04 | Johns Manville | Formaldehyde-free melamine carbohydrate binders for improved fire-resistant fibrous materials |
US9982082B2 (en) | 2014-07-03 | 2018-05-29 | Johns Manville | Formaldehyde-free melamine carbohydrate binders for improved fire-resistant fibrous materials |
Also Published As
Publication number | Publication date |
---|---|
LU60096A1 (tr) | 1970-06-26 |
FI50250B (tr) | 1975-09-30 |
NL6919597A (tr) | 1970-07-02 |
GB1289860A (tr) | 1972-09-20 |
NL137596C (tr) | |
DE1965373B2 (de) | 1974-04-04 |
NO129681B (tr) | 1974-05-13 |
SE365269B (tr) | 1974-03-18 |
FR1602233A (tr) | 1970-10-26 |
DE1965373A1 (de) | 1970-07-30 |
BE743673A (tr) | 1970-06-24 |
DK132089C (da) | 1976-03-15 |
DK132089B (da) | 1975-10-20 |
SE377477B (tr) | 1975-07-07 |
DE1965373C3 (de) | 1974-11-07 |
FI50250C (fi) | 1976-01-12 |
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