CA1119758A - Use of polyimide amine salts as cationic surface sizing agents for paper - Google Patents
Use of polyimide amine salts as cationic surface sizing agents for paperInfo
- Publication number
- CA1119758A CA1119758A CA000307675A CA307675A CA1119758A CA 1119758 A CA1119758 A CA 1119758A CA 000307675 A CA000307675 A CA 000307675A CA 307675 A CA307675 A CA 307675A CA 1119758 A CA1119758 A CA 1119758A
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- paper
- sizing
- acid
- parts
- sizing agent
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Classifications
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Salts of organic or inorganic acids with polyimide amines wherein the polyimide amines are obtained by reaction of copolymers of maleic acid anhydride and 2, 4, 4-trimethyl-1-pentene with a mixture of a diamine having a tertiary and a primary amino group and ammonia or a primary monoamine and at least 80% of the anhydride groups having been converted into the corresponding imide groups are used as surface sizing agents for paper.
Salts of organic or inorganic acids with polyimide amines wherein the polyimide amines are obtained by reaction of copolymers of maleic acid anhydride and 2, 4, 4-trimethyl-1-pentene with a mixture of a diamine having a tertiary and a primary amino group and ammonia or a primary monoamine and at least 80% of the anhydride groups having been converted into the corresponding imide groups are used as surface sizing agents for paper.
Description
5t~
This invention relates to the use of salts of poly-imide amines with organic or inorganic acids for the surface sizing of paper and to surface sizing agents derived therefrom.
The polyimide amines are derived from copolymers of maleic acid anhydride and 2, 4, 4-trimethyl-1-pentene.
It is known from D~S No. 1,570,914 ( Belgian Patent No. 654,889) that maleic acid anhydride copolymers containing unsaturated monomers such as, for example, styrene, vinyl and allyl ethers, and unbranched ~ olefins as comonomers, can be reacted with a diamine and optionally a monoamine.
The diamine contains both a primary and also a tertiary amino group, and the reaction is carried out in inert organic solvents. lhe polyimide amines obtained thereby are quaternized with epihalohydrins, for example epichlorohydrin. These quaternized p:roducts are used in aqueous solution as surface sizing agents for paper. The polymers have molecular weights of from 2000 to 5000. With higher molecular weights gelation occurs and with products of very low molecualr weight ~below 2000), the sizing effect is inadequate.
It is known from German Patent No. 1,5959704 that maleic acid anhydride homopolymers or copolymers can be reacted with a mixture of diamines containing a primary and a tertiary amino group and primary monoamines. In this case, there is approxlma~tely one primary amino group for each anhydride group, and the reaction is carried out at elevated ~ 1119758 temperature in aqueous or alcoholic-aqueous acids. From 25 to 350 mole % of acid equivalents are used, based on tertiary amino groups in the amine mixture. The polyimide amines thus produced are suitable in neutral form as emulsifiers and dispersants for the production of coatings and protective coatings. They are also suitable for use as hydrophobing agents and as intermediate products for plant protection agents and pharmaceuticals.
For the production of paper sizing agents, polyimide amines of ~he type known either have to be mixed with non-cationic polymers ~German Patent No. 1,621,68B) or converted -into graft polymers with special olefinically unsaturated graft monomers ~German Patent No. 1,621,689). As can be seen from the comparison tests in German Patent No.
1,621,688, the polyimide amines when used on their own -.~ ..
have a distinctly weaker, and inadequate sizing effect.
It has now surprisingly been found that polyimide amines of the above-mentioned type, which are derived from copolymers of maleic acid anhydride and 2,4,4-trimethyl-1-~' 20 pentene by reaction with a mixture of diamine containing a `~ tertiary and primary amino group and a primary monoamine, may be used directly in the form of an aqueous solution of their organic or inorganic acid salts as extremely effective - surface sizing agents for paper.
Accordingly, the present invention provides the use of salts of organic or inorganic acids with polyimide amines derived from copolymers of maleic acid anhydride and 2,4,4-.'' ~:
~i ., . ~ 3 ~ . . .
'75~3 trimet}lyl-l-pentene by reaction with a mi~ture of a diamine contain-ing a tertiary and a primary amino group and a;nmonia Ol a primary monoamine as surface sizing agents for paper and paper-like materials.
The present invention likewise provides a process for sizing paper wherein the afore-mcntioned salts are used as sizing agents.
The copolymers of maleic acid anhydride with 2,4,4-trimethyl-l-pentene preferably have an equimolar, alternating structure. Their average molecular weights are between 8000 and 500,000 and preferably between 10,000 and 60,000, as determined by membrane osmometry. The preferred copolymers have intrinsic viscosities of from 0.08 to 0.3 dl/g, as measured in N, N-dimethyl formamide at 25C.
Copolymers having intrinsic viscosities of less than 0.08 dl/g are far less effective sizing agents for paper.
Products of excessively high molecular weight lead to excessive viscosities of the sizing agent and, hence, to poorer processibility.
For producing the polyimide amines, the copolymers of maleic acid anhydride and 2,4,4-trimethyl-1-pentene are reacted in an anhydrous organic medium with a mixture of A) a diamine containing a primary and a tertiary amino group and ~) ammonia or a primary monoamine at temp-eraturesof from 0 to 250C and at least 80% and preferably more than 85% of the anhydride groups in the copolymers are converted in-to the corresponding imide groups.
The molar ratio of diamine (A) to monoamine (B) is between 1: 0.~ and 1: 2Ø
~. r . . . ~
The diamines used have the general formula (~) (A) and the monoamines used have the general formula ~B) ~B) R3-NH2.
e formulae, R is a C2 - C12, preferably C2 ~ C6, linear or branched aliphatic chain which may optionally contain oxygen or sulphur atoms. The substituents Rl and R2 of the tertiary amino group may be the same or different and each represents an aromatic radical, such as phenyl, tolyl, xylyl, chlorophenyl, nitrophenyl, and 4-dimethylaminophenyl, but preferably phenyl, tolyl, and xylyl, an araliphatic radical, such as benzyl, and 2-phenylethyl, but preferably benzyl, an alkyl radical having from 1 to 12 and preferably from 1 to 6 carbon atoms, or the two substituents Rl and R2 together may form a 5-membered or 6-membered cyclic ring optionally containing an oxygen or sulphur atom.
Preferred diamines are those in which the primary and tertiary amino group are separated from each other by a linear alkylene chain having from 2 to 6 me~hylene groups and of which the tertiary amino group is substituted by linear Cl-C4-alkyl radicals. l~Amino-3-dimethylaminopropane is particularly preferred. It is however, also possible to use . mixtures of the afore-mentioned diamines.
The substituent R3 is a saturated or unsaturated aliphatic or cycloaliphatic optionally substituted hydro-carbon radical.
Preferred monoamines are ammonia, aliphatic primary monoamines having from 1 to 18 carbon atoms, cycloaliphatic monoamines having from 5 to 8 carbon atoms or mixtures thereof.
Particularly preferred monoamines are, for example, methyl-amine, ethylamine, n-propylamine~ n ^butylamine, sec.-butyl-amine, iso-butylamine, tert.-bu~ylamine, n-hexylamine,
This invention relates to the use of salts of poly-imide amines with organic or inorganic acids for the surface sizing of paper and to surface sizing agents derived therefrom.
The polyimide amines are derived from copolymers of maleic acid anhydride and 2, 4, 4-trimethyl-1-pentene.
It is known from D~S No. 1,570,914 ( Belgian Patent No. 654,889) that maleic acid anhydride copolymers containing unsaturated monomers such as, for example, styrene, vinyl and allyl ethers, and unbranched ~ olefins as comonomers, can be reacted with a diamine and optionally a monoamine.
The diamine contains both a primary and also a tertiary amino group, and the reaction is carried out in inert organic solvents. lhe polyimide amines obtained thereby are quaternized with epihalohydrins, for example epichlorohydrin. These quaternized p:roducts are used in aqueous solution as surface sizing agents for paper. The polymers have molecular weights of from 2000 to 5000. With higher molecular weights gelation occurs and with products of very low molecualr weight ~below 2000), the sizing effect is inadequate.
It is known from German Patent No. 1,5959704 that maleic acid anhydride homopolymers or copolymers can be reacted with a mixture of diamines containing a primary and a tertiary amino group and primary monoamines. In this case, there is approxlma~tely one primary amino group for each anhydride group, and the reaction is carried out at elevated ~ 1119758 temperature in aqueous or alcoholic-aqueous acids. From 25 to 350 mole % of acid equivalents are used, based on tertiary amino groups in the amine mixture. The polyimide amines thus produced are suitable in neutral form as emulsifiers and dispersants for the production of coatings and protective coatings. They are also suitable for use as hydrophobing agents and as intermediate products for plant protection agents and pharmaceuticals.
For the production of paper sizing agents, polyimide amines of ~he type known either have to be mixed with non-cationic polymers ~German Patent No. 1,621,68B) or converted -into graft polymers with special olefinically unsaturated graft monomers ~German Patent No. 1,621,689). As can be seen from the comparison tests in German Patent No.
1,621,688, the polyimide amines when used on their own -.~ ..
have a distinctly weaker, and inadequate sizing effect.
It has now surprisingly been found that polyimide amines of the above-mentioned type, which are derived from copolymers of maleic acid anhydride and 2,4,4-trimethyl-1-~' 20 pentene by reaction with a mixture of diamine containing a `~ tertiary and primary amino group and a primary monoamine, may be used directly in the form of an aqueous solution of their organic or inorganic acid salts as extremely effective - surface sizing agents for paper.
Accordingly, the present invention provides the use of salts of organic or inorganic acids with polyimide amines derived from copolymers of maleic acid anhydride and 2,4,4-.'' ~:
~i ., . ~ 3 ~ . . .
'75~3 trimet}lyl-l-pentene by reaction with a mi~ture of a diamine contain-ing a tertiary and a primary amino group and a;nmonia Ol a primary monoamine as surface sizing agents for paper and paper-like materials.
The present invention likewise provides a process for sizing paper wherein the afore-mcntioned salts are used as sizing agents.
The copolymers of maleic acid anhydride with 2,4,4-trimethyl-l-pentene preferably have an equimolar, alternating structure. Their average molecular weights are between 8000 and 500,000 and preferably between 10,000 and 60,000, as determined by membrane osmometry. The preferred copolymers have intrinsic viscosities of from 0.08 to 0.3 dl/g, as measured in N, N-dimethyl formamide at 25C.
Copolymers having intrinsic viscosities of less than 0.08 dl/g are far less effective sizing agents for paper.
Products of excessively high molecular weight lead to excessive viscosities of the sizing agent and, hence, to poorer processibility.
For producing the polyimide amines, the copolymers of maleic acid anhydride and 2,4,4-trimethyl-1-pentene are reacted in an anhydrous organic medium with a mixture of A) a diamine containing a primary and a tertiary amino group and ~) ammonia or a primary monoamine at temp-eraturesof from 0 to 250C and at least 80% and preferably more than 85% of the anhydride groups in the copolymers are converted in-to the corresponding imide groups.
The molar ratio of diamine (A) to monoamine (B) is between 1: 0.~ and 1: 2Ø
~. r . . . ~
The diamines used have the general formula (~) (A) and the monoamines used have the general formula ~B) ~B) R3-NH2.
e formulae, R is a C2 - C12, preferably C2 ~ C6, linear or branched aliphatic chain which may optionally contain oxygen or sulphur atoms. The substituents Rl and R2 of the tertiary amino group may be the same or different and each represents an aromatic radical, such as phenyl, tolyl, xylyl, chlorophenyl, nitrophenyl, and 4-dimethylaminophenyl, but preferably phenyl, tolyl, and xylyl, an araliphatic radical, such as benzyl, and 2-phenylethyl, but preferably benzyl, an alkyl radical having from 1 to 12 and preferably from 1 to 6 carbon atoms, or the two substituents Rl and R2 together may form a 5-membered or 6-membered cyclic ring optionally containing an oxygen or sulphur atom.
Preferred diamines are those in which the primary and tertiary amino group are separated from each other by a linear alkylene chain having from 2 to 6 me~hylene groups and of which the tertiary amino group is substituted by linear Cl-C4-alkyl radicals. l~Amino-3-dimethylaminopropane is particularly preferred. It is however, also possible to use . mixtures of the afore-mentioned diamines.
The substituent R3 is a saturated or unsaturated aliphatic or cycloaliphatic optionally substituted hydro-carbon radical.
Preferred monoamines are ammonia, aliphatic primary monoamines having from 1 to 18 carbon atoms, cycloaliphatic monoamines having from 5 to 8 carbon atoms or mixtures thereof.
Particularly preferred monoamines are, for example, methyl-amine, ethylamine, n-propylamine~ n ^butylamine, sec.-butyl-amine, iso-butylamine, tert.-bu~ylamine, n-hexylamine,
2-ethylhexylamine, cyclohexylamine and dehydroabietylamine.
A particularly preferred amine mixture consists of l-amino-3-dimethylaminopropane and ethylamine in a molar ratio of from 1:1 to 1:1.6.
The mixture of the diamines (A) and the monoamines (B) is used in a substantially equimolar quantity, but preferably in a small excess, based on the anhydride groups in the starting polymer. The amine mixture used should preferably contain from l.0 to 1.5 moles of primary amino groups per mole of anhydride groups in the polymer. The amine excess is added to obtain as complete an imidation as possible and this should amount to at least 80% and preferably to more than 85%. Reaction products having a lower degree of imidation are difficult to dissolve in water and generally show an inadequate sizing effect on paper. In the mixture of diamine (A) and primary amine (B), the molar ratio of diamine to monoamine should amount to between 1:0.3 and 1:2Ø The two amine components may be reacted either in admixture or successively. Suitable solvents are inter alia organic alkyl-"~ - 6 -and halogen-substituted aromatic solvents, such as benzene, toluene, m, o- or p-xylene or mixtures thereof. They are capable of dissolving both the maleic acid anhydride-2,4,4-trimethyl-l-pentene copolymers and also their reaction products, that is, the polyimide amines.
To produce the sizing agents and to dissolve the polyimide amines in aqueous systems, the polyimide amines have to be converted into salt form. Inorganic or organic acids are suitable for this purpose, and are added in quantities of from 100 to 500 mole %, based on the tertiary amino groups present in the chemically bound amine mixture. Suitable acids are, in particular, formic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, nitric acid and sulphuric acid, but preferalby formic acid or acetic acid. Water is -generally used as solvent. On completion of the reaction, ~ ~
the polyimide amine salts are normally present in the form of ~`
a 5 to 30% solution. The products show no signs of the gelation described in Belgian Patent Specification No. 654,889 in the relatively high molecular weight range above 5000.
Imidation of the copolymer of maleic acid anhydride and 2,4,4-trimethyl-1-pentene is preferably carried out in two steps. In the first step, the copolymer is suspended or dissolved in the organic solvent at temperatures of from 0C -~
to 50C and the amine mixture is added dropwise with stirring -:
at the same temperatures. This step of the reaction results predominantly in the formation of the monoamide. In the second step of the reaction, the reaction mixture is heated with stirring to a temperature of from 130 to 200C. This step, in which imide formation takes place from at least 80 % and - : , :-: ~. . : . , .- .
- . . , - .. . :
`~ 111~758 ~` preferably from more than 85 % of the original anhydride groups, is carried out thermally, optionally in the presence of catalysts, such as for example p-taluene sulph~nic acid~ or pyridine, with elimination of water.
The organic polymer solution may be converted into an aqueous polymer solution by for example continuously introducing said organic solution in a heated receiver containing dilute aqueous acid with simultaneous removal of the organic solvent by distillation.
In contrast to the teaching of German Patent Specification No. 1,595,704, the copolymers of maleic acid anhydride and 2,4,4-trimethyl-1-pentene reacted to form polyimide amine salts are used in the present invention as surface sizing agents for paper having excellent sizing effect in aqueous solution alone, i.e. without any need for additives. In contrast to hydrophobing agents, which have a water-repelling effect, sizing agents are products which enable paper to be written on with ink without the ink runni~g. Whereas therefore hydrophobising agents are water-repellent and insoluble in water, the sizing agents of the present invention are soluble in water.
In addition, it has been found that the process described in German Patent Specifications Nos. 1,595,704 and 1,621,688 for producing polyimide amines is not suitable for the sizing agents used in the present invention, because said process gives products which do not even remotely approach th~ required high degree of imidation of at least 80 %. Thus, salts of these products with acids are also unsuitable for use as sizing agents for paper.
~1197S8 One advance over German Patent Specification No.
1,621,688. in which cationic sizing agents are used in the form of dispersions, is the fact that, in the present invention, the sizing agents are used in homogeneous aqueous solution.
They can be processed without difficulty, guarantee absolute homogeneity of the sized paper in contrast to the hetero- ~
geneous sizing systems, and show an outstanding sizing -effect on papers of all kinds, the sizing of chalk-containing paper being particularly effective. The sizing agents used in the presentinvention are clearly superior in this respect to all conventional sizing agents. -The parts quoted in the following illustrative Examples represent parts by weight unless otherwise stated. --EXAMPLE A
In a three-necked flask equipped with a water separator, ;
105 parts of an alternating copolymer of maleic acid anhydride and 2,4,4-trimethyl-1-pentene ~average molecular weight GPC 47,000) is introduced into 260 parts of xylene. The copolymer is dissolved with stirring at 120C, followed by the successive dropwlse addition of 26 parts of dehydro-abietylamine dlssolved in 174 parts of xylene and 63 parts of l-amino-3-dimethylaminopropane. The mixture is then left to react for 10 hours at 150 to 160C while using the water separator. ~
The quantity of water separated off during the azeotropic ;
distillation with xylene is regarded as an approximate measure -1) MGPC = molecular weight as determined by gel permeation chromatography :.. ,, . ,, ,. ,- . :
,.: .. , , : :: . ., , ,- . . . .
~119758 of the conversion (8.5 ml = 94~ conversion). On completion of polyimide formation, 50 parts of formic acid are added dropwise. Most of the xylene is decanted off from the precipitating polyimide amine salt, the rest of the solvent being azeotropically distilled off with steam. At the same time, an aqueous solution with a solids content oi 9.1 by weight is obtained.
EXAMPLE B
105 parts of copolymer of maleic acid anhydride and 2,4,4-trimethyl-1-pentene (MGpC= 47,000) is dissolved in 260 parts of xylene at 120C. A mixture of 45 parts of stearylamine and 34 parts of 1-amino-3-dimethylaminopropane dissolved in 174 parts of xylene is added dropwise with stirring to the polymer solution. A product insoluble in xylene, probably the monoamide, is initially obtained during the highly exothermic reaction, being converted into the soluble polyimide amine with elimination of water by stirrlng for 10 hours at 150 to 160C ~ile usin~ the water separator.
Formation of the polyimide amine can be recognized very easily from the IR-double band characteristic oi cyclic five-ring imides at 1690 cm 1 and 1770 cm 1, whilst the partial band characteristic of cyclic five-ring anhydrides at 1840 cm 1 disappears. 34.5 parts of iormic acid are then added dropwise. The organic solvent is distilled oi~ with steam at 100C. The aqueous solution has a solids content of 14.9 ~ by weight.
.
Le A 18 058 - 10 -- ; :; : l : , . . ::
EXAMPLE C
The procedure is as in Example B, except that, instead of the amine mixture used in Example B, a mixture of 46 parts of dodecylamine and 26 parts of 1-amino-3-dimethylamino-propane dissolved in 174 parts of xylene is added dropwise.
The aqueous solution has a solids content of 10.5 % by weight.
EXAMPLE D
The procedure is as in Example B except that, instead of the amine mixture used in Example B, a solvent-free mixture of 15 parts of hexylamine and 39 parts of l-amino-
A particularly preferred amine mixture consists of l-amino-3-dimethylaminopropane and ethylamine in a molar ratio of from 1:1 to 1:1.6.
The mixture of the diamines (A) and the monoamines (B) is used in a substantially equimolar quantity, but preferably in a small excess, based on the anhydride groups in the starting polymer. The amine mixture used should preferably contain from l.0 to 1.5 moles of primary amino groups per mole of anhydride groups in the polymer. The amine excess is added to obtain as complete an imidation as possible and this should amount to at least 80% and preferably to more than 85%. Reaction products having a lower degree of imidation are difficult to dissolve in water and generally show an inadequate sizing effect on paper. In the mixture of diamine (A) and primary amine (B), the molar ratio of diamine to monoamine should amount to between 1:0.3 and 1:2Ø The two amine components may be reacted either in admixture or successively. Suitable solvents are inter alia organic alkyl-"~ - 6 -and halogen-substituted aromatic solvents, such as benzene, toluene, m, o- or p-xylene or mixtures thereof. They are capable of dissolving both the maleic acid anhydride-2,4,4-trimethyl-l-pentene copolymers and also their reaction products, that is, the polyimide amines.
To produce the sizing agents and to dissolve the polyimide amines in aqueous systems, the polyimide amines have to be converted into salt form. Inorganic or organic acids are suitable for this purpose, and are added in quantities of from 100 to 500 mole %, based on the tertiary amino groups present in the chemically bound amine mixture. Suitable acids are, in particular, formic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, nitric acid and sulphuric acid, but preferalby formic acid or acetic acid. Water is -generally used as solvent. On completion of the reaction, ~ ~
the polyimide amine salts are normally present in the form of ~`
a 5 to 30% solution. The products show no signs of the gelation described in Belgian Patent Specification No. 654,889 in the relatively high molecular weight range above 5000.
Imidation of the copolymer of maleic acid anhydride and 2,4,4-trimethyl-1-pentene is preferably carried out in two steps. In the first step, the copolymer is suspended or dissolved in the organic solvent at temperatures of from 0C -~
to 50C and the amine mixture is added dropwise with stirring -:
at the same temperatures. This step of the reaction results predominantly in the formation of the monoamide. In the second step of the reaction, the reaction mixture is heated with stirring to a temperature of from 130 to 200C. This step, in which imide formation takes place from at least 80 % and - : , :-: ~. . : . , .- .
- . . , - .. . :
`~ 111~758 ~` preferably from more than 85 % of the original anhydride groups, is carried out thermally, optionally in the presence of catalysts, such as for example p-taluene sulph~nic acid~ or pyridine, with elimination of water.
The organic polymer solution may be converted into an aqueous polymer solution by for example continuously introducing said organic solution in a heated receiver containing dilute aqueous acid with simultaneous removal of the organic solvent by distillation.
In contrast to the teaching of German Patent Specification No. 1,595,704, the copolymers of maleic acid anhydride and 2,4,4-trimethyl-1-pentene reacted to form polyimide amine salts are used in the present invention as surface sizing agents for paper having excellent sizing effect in aqueous solution alone, i.e. without any need for additives. In contrast to hydrophobing agents, which have a water-repelling effect, sizing agents are products which enable paper to be written on with ink without the ink runni~g. Whereas therefore hydrophobising agents are water-repellent and insoluble in water, the sizing agents of the present invention are soluble in water.
In addition, it has been found that the process described in German Patent Specifications Nos. 1,595,704 and 1,621,688 for producing polyimide amines is not suitable for the sizing agents used in the present invention, because said process gives products which do not even remotely approach th~ required high degree of imidation of at least 80 %. Thus, salts of these products with acids are also unsuitable for use as sizing agents for paper.
~1197S8 One advance over German Patent Specification No.
1,621,688. in which cationic sizing agents are used in the form of dispersions, is the fact that, in the present invention, the sizing agents are used in homogeneous aqueous solution.
They can be processed without difficulty, guarantee absolute homogeneity of the sized paper in contrast to the hetero- ~
geneous sizing systems, and show an outstanding sizing -effect on papers of all kinds, the sizing of chalk-containing paper being particularly effective. The sizing agents used in the presentinvention are clearly superior in this respect to all conventional sizing agents. -The parts quoted in the following illustrative Examples represent parts by weight unless otherwise stated. --EXAMPLE A
In a three-necked flask equipped with a water separator, ;
105 parts of an alternating copolymer of maleic acid anhydride and 2,4,4-trimethyl-1-pentene ~average molecular weight GPC 47,000) is introduced into 260 parts of xylene. The copolymer is dissolved with stirring at 120C, followed by the successive dropwlse addition of 26 parts of dehydro-abietylamine dlssolved in 174 parts of xylene and 63 parts of l-amino-3-dimethylaminopropane. The mixture is then left to react for 10 hours at 150 to 160C while using the water separator. ~
The quantity of water separated off during the azeotropic ;
distillation with xylene is regarded as an approximate measure -1) MGPC = molecular weight as determined by gel permeation chromatography :.. ,, . ,, ,. ,- . :
,.: .. , , : :: . ., , ,- . . . .
~119758 of the conversion (8.5 ml = 94~ conversion). On completion of polyimide formation, 50 parts of formic acid are added dropwise. Most of the xylene is decanted off from the precipitating polyimide amine salt, the rest of the solvent being azeotropically distilled off with steam. At the same time, an aqueous solution with a solids content oi 9.1 by weight is obtained.
EXAMPLE B
105 parts of copolymer of maleic acid anhydride and 2,4,4-trimethyl-1-pentene (MGpC= 47,000) is dissolved in 260 parts of xylene at 120C. A mixture of 45 parts of stearylamine and 34 parts of 1-amino-3-dimethylaminopropane dissolved in 174 parts of xylene is added dropwise with stirring to the polymer solution. A product insoluble in xylene, probably the monoamide, is initially obtained during the highly exothermic reaction, being converted into the soluble polyimide amine with elimination of water by stirrlng for 10 hours at 150 to 160C ~ile usin~ the water separator.
Formation of the polyimide amine can be recognized very easily from the IR-double band characteristic oi cyclic five-ring imides at 1690 cm 1 and 1770 cm 1, whilst the partial band characteristic of cyclic five-ring anhydrides at 1840 cm 1 disappears. 34.5 parts of iormic acid are then added dropwise. The organic solvent is distilled oi~ with steam at 100C. The aqueous solution has a solids content of 14.9 ~ by weight.
.
Le A 18 058 - 10 -- ; :; : l : , . . ::
EXAMPLE C
The procedure is as in Example B, except that, instead of the amine mixture used in Example B, a mixture of 46 parts of dodecylamine and 26 parts of 1-amino-3-dimethylamino-propane dissolved in 174 parts of xylene is added dropwise.
The aqueous solution has a solids content of 10.5 % by weight.
EXAMPLE D
The procedure is as in Example B except that, instead of the amine mixture used in Example B, a solvent-free mixture of 15 parts of hexylamine and 39 parts of l-amino-
3-dimethylaminopropane is added dropwise. The aqueous solution has a solids content of 13.5 % by weight.
EXAMPLE E
105 parts of copolymer of maleic acid anhydride and 2,4,4-trinethyl-1-pentene is dissolved in 435 parts of -xylene at 120C, followed by dropwise addition of a mixture of 22 parts of cyclohexylamine and 28 parts of l-amino-3-dimethylaminopropane. 8.3 parts of water are separated off in the water separator ~= 92 % conversion). Thereafter 35 parts of formic acid are added, followed by distillation with steam at 100C. The aqueous solution has a solids content of 7.9 %.
EXAMPLE F
525 parts of the same copolymer as in Example A, 200 parts of xylene, 91 parts of n-butylamine and 128 parts of l-amino-3-dimethylaminopropane are introduced into a stirrer-equipped fine steel autoclave. After heating with stirring to 50C, the mixture is kept at that temperature for 2 hours . . , . , - - .
11~9758 and is then stirred for 3 hours at 130C. 42.5 parts of water are separated off in the water separator (= 94~
conversion). 250 parts of formic acid are then added to the solution and the xylene is azeotropically distilled off with steam. The aqueous solution has a solids content oi 11.4 ~.
EXAMPLE G
525 parts of the same copolymer as in Example A, dissolved in 525 parts of toluene, is introduced into a stirrer-equipped autoclave toget~er with 1650 parts of xylene, 85 parts o~ 1-amino-3-dimethylaminopropane and 98 parts of n-propylamine, followed by stirring for 3 hours at 50C and then for 7 hours at 130C. 40 parts of water are separated off in the water separator (= 890h conversion).
173 parts of formic acid are added dropwise to the so~ution of the polyimide amine, followed as before by distillation with steam. The aqueous solution has a solids content of 6.5 oh~
EXAMPLE H
The procedure is as in Example G except that, instead of n-propylamine and 1-amino-3-dimethylaminopropane, a mixture of 126 parts of ethylamine and 112 parts of 1-amino-3-di-methylaminopropane is used. The aqueous solution has a solids content of 9.6 oh~
EXAMPLE I
814 parts of the same copolymer as in Example A is introduced into a stirrer-equippea autoclave together with 3100 p~s of xylene, 181 oarts of 1-amino-3-dimethylaminopropane and 112 parts of ethylamine. The mixture is then stirred ~or Le A 18 058 - 12 -. ~ , . . .
. ~
~119758 3 hours at 50C and for 7 hours at 130C. 65 parts of water are separated in the water separator ~= 93% conversion).
380 parts of formic acid are added dropwise to the solution of the polyimide amine, followed by distillation with steam.
The aqueous solution has a solids content of 10.8% and a -viscosity at 25C of approximately 30 cP, as measured in a Haake Viscotester.
The use of sizing agents A - H is described by way of example in the following:
The sizing solution used for surface sizing consisted of -a solution of 5% by weight of starch (Perfectamyl A 4692, a product of the AVEBE company) and 0.25% by weight or, in some cases, 0.5% by weight of the sizing agent to be ~~
tested (expressed as active substance) in 94.75% by weight or 94.5% by weight of water.
A laboratory sizing press of the type manufactured by the Werner Mathis company of Zurich (type HF) was used for sizing. The sizing solution had a temperature of approximately 20~C in the sizing press. The paper was drawn through the sizing press at a rate of 4 metres per minute.
The surface-sized papers were dried in 45 seconds at about 100C on a drying cylinder. Before the sizing test, the papers were conditioned for 2 hours at ambient temperature.
Pieces of the paper were then preweighed, immersed for 1 `
minute in water at 20C, squeezed oncebetween filter paper under the weight of a 10 kg roll and then reweighed. The value for the absorption of water on both sides was calculated .~
-''i''7~
~J
-. ~ . ,-, :, ~ - .
~19758 in g/m2 from the difference ln weight The lower the water absorption, the better the effect o~ the tested sizing agent. A good sizing eXfect i9 shown by a water absorption of about 40 g/m2 or less.
This Example is intended to demonstrate that good sizing effects can be obtained with the described sizing agents on unsized papers o~ bleached pulps.
The raw paper used had been produced ~rom bleached sulphite pulp with the addition o~ 3 ~ of China Clay (expressed as ash) at pH 6.8 and had a weight per unit area Or 70 g/m2.
: Table 1:
Surface sizing on unsized paper of bleached ~ulp Water absorption in g/m2 with addition of Sizing agent 0.25 ~ by weight 0.5 ~ by weight of sizing~agent (based on pure active substance) to the sizing solution:
: ~ A 38.0 B 56.8 38.1 ~: C 57.7 40.0 ; D 43.9 E 44.2 F 39.9 In the absence of sizing agent, water absorption is : 87 g/m .
This Example demonstrates the ei~ectiveness o~ the described sizing agents on papers containing mechanical wood pulp. The raw paper used had been produced from 50 ~
bleached mechanical wood pulp and 50 ~ bleached sulphite Le A 18 058 _ 14 _ 1119'7~i~
p u l p W i t. ll t}~ e a d d i t, i O I~ O f I 1 ~lo () I ( ~ h ~ l y ( . ~ 1 ', ash) A t p~l 5 and ha~l a we i gil t ~)cr ulli t al`cSl 1~1 7(; ~r;/m~~
Table 2~
__ Surface sizing on unsized paper eontai~ n" mechaJ~ic~:t wood pulp Si~ing agent Water absorption i.n g/m wi,th addition of O . 25 /0 hy ~eight 0 . 5 /0 by weight of sizing agent (based on pure ac ti-ve subs tance~
to the si~;ing solution:
3!~ 0 B 68 4 37. 6 C 55 . l 34 ~ 8 D 33.3 E 34.5 F 31.0 G 31~2 H 31.0 In the absence OI sizing agen-t, water absorption is 92 . 7 g/m This Example demonstrates the favourable e~fec-t of the described siz.ing agents on papers containing cal cium carbonate ~
The raw paper used had been prod-uced from 51) /0 bl.eached pine sulphite and 50 /0 bleached beech sulphate pulp with the addition of 14 /0 precipitated ca:l ci~n carbonate ( e2~pressed as ash) at lpH 6 . 8 and had a weight per unit area of 70 g/m 0 Le A 18 058 - 15 -~975B
Table 3:
Surface sizing on unsized paper containing calcium carbonate Sizin~ agent Water absorption in g/m2 with addition of 025 ~ by weight 0.5 ~ by weight of sizing agent (based on pure active substance to the sizing solution:
A 37.0 B 53.4 31.8 C 54.5 44.5 D 32.8 E 35.7 F 32.6 G 33.5 H 34.6 In the absence of sizing agent, water absorption amounts to 77.6 g/m .
In this Example, one of the described products, sizing agent J, is compared with a cationic "sizing agent M"
which represents the prior art and which corresponds in its composition to the products described in G~En Patent Nb.
1,621,688.
The following raw papers were used:
20 Raw paper I: as described in Example 1 " II: as described in Example 3 III: bleached pulp, approximately 12 ~ oi talcum ash, 1 ~ of aluminium sulphate, unsized; approx.
80 g/m 25: " IV: bleached pulp, approximately 7 ~ China Clay ash, presized with 0.1 ~ o~ resin size and 0.5 oi aluminium sulphate; approx. 75 g/m2.
The degree of sizing against ink was determined by means o~ a Hercules Sizing Tester in accordance with the operating instructions of the~manuiacturers, Hercules Inc., Le A 18 058 - 16 -'.' ' ~'. - , - - `.: ~`''. ' `; ' `.
. .
~9758 Wilmington, Delaware, USA. The test apparatus used measures th0 period of time in seconds which is required for the remission value to fall to 75% of the remission value of paper when the test ink is applied to the paper and penetrates through it. The longer the time measured, the better the degree of sizing.
Table 4:
Comparison of one of the described products, sizing agent J, with a standard commercial-grade sizing agent M on various papers ~ -~
Paper: Sizing agent: Degree of sizing with addition of 0.125 0.175 0.25 % by weight of active substance to the solution: -.
I Comparison M79 177 352 secs.
Sizing agent J 144 344 401 secs.
II Comparison M19 69 152 secs.
Sizing agent 1 77 231 298 secs.
III Comparison M129 424 532 secs.
Sizing agent J 245 619 816 secs.
IV Comparison M42 130 304 secs.
Sizing agent J 194 237 414 secs.
It can clearly be seen that, in all the unsized and presized papers tested, the sizing effect of sizing agent J
is considerably superior to that of the standard commercial-grade sizing agent M in the three practical concentrations selected.
This Example demonstrates the suitability of the described sizing agents for use in pulp.
1 % and 2 % of sizing agent ~active substance, based on dry pulp) were added with stirring to a pulp of 50 % of birch sulphate, 30 % of pine sulphate and 20 % of spruce .. . .
., - - ; . :~ -- . : . -- , ~ ., sulphite pulp (pulp density 0.5 ~) at a pH-value of 6.9.
Sheets of paper were then immediately formed on a laboratory sheet former and dried at 100C. The paper had a weight per unit area of approximately 100 g/m2.
The sizing effect was determined by the "ink float test"
normally applied in the paper industry, i.e. by applying the papers to test ink (Pelikan 4001).
A cationic "sizing agent M", corresponding to the products described in German Patent No. 1,621,688, was again used for comparison.
Table 5:
Comparison of the described sizing agents with a standard commercial grade sizing agent M when used in pulp Sizing agent: Ink float test: no penetration of ink through paper pulp-sized with 1 ~ by weight 2 /0 by weight Sizing agent M 10 mins after 20 mins.
" A 10 mins. 20 mins.
" B 10 mins. 20 mins.
C 1 min. 2 mins.
D 5 min~. 20 mins.
" E 10 mins. 20 mins.
" G 10 mins. 20 mins.
" H 10 mins. 20 mins.
Le A 18 05~ - 18 -
EXAMPLE E
105 parts of copolymer of maleic acid anhydride and 2,4,4-trinethyl-1-pentene is dissolved in 435 parts of -xylene at 120C, followed by dropwise addition of a mixture of 22 parts of cyclohexylamine and 28 parts of l-amino-3-dimethylaminopropane. 8.3 parts of water are separated off in the water separator ~= 92 % conversion). Thereafter 35 parts of formic acid are added, followed by distillation with steam at 100C. The aqueous solution has a solids content of 7.9 %.
EXAMPLE F
525 parts of the same copolymer as in Example A, 200 parts of xylene, 91 parts of n-butylamine and 128 parts of l-amino-3-dimethylaminopropane are introduced into a stirrer-equipped fine steel autoclave. After heating with stirring to 50C, the mixture is kept at that temperature for 2 hours . . , . , - - .
11~9758 and is then stirred for 3 hours at 130C. 42.5 parts of water are separated off in the water separator (= 94~
conversion). 250 parts of formic acid are then added to the solution and the xylene is azeotropically distilled off with steam. The aqueous solution has a solids content oi 11.4 ~.
EXAMPLE G
525 parts of the same copolymer as in Example A, dissolved in 525 parts of toluene, is introduced into a stirrer-equipped autoclave toget~er with 1650 parts of xylene, 85 parts o~ 1-amino-3-dimethylaminopropane and 98 parts of n-propylamine, followed by stirring for 3 hours at 50C and then for 7 hours at 130C. 40 parts of water are separated off in the water separator (= 890h conversion).
173 parts of formic acid are added dropwise to the so~ution of the polyimide amine, followed as before by distillation with steam. The aqueous solution has a solids content of 6.5 oh~
EXAMPLE H
The procedure is as in Example G except that, instead of n-propylamine and 1-amino-3-dimethylaminopropane, a mixture of 126 parts of ethylamine and 112 parts of 1-amino-3-di-methylaminopropane is used. The aqueous solution has a solids content of 9.6 oh~
EXAMPLE I
814 parts of the same copolymer as in Example A is introduced into a stirrer-equippea autoclave together with 3100 p~s of xylene, 181 oarts of 1-amino-3-dimethylaminopropane and 112 parts of ethylamine. The mixture is then stirred ~or Le A 18 058 - 12 -. ~ , . . .
. ~
~119758 3 hours at 50C and for 7 hours at 130C. 65 parts of water are separated in the water separator ~= 93% conversion).
380 parts of formic acid are added dropwise to the solution of the polyimide amine, followed by distillation with steam.
The aqueous solution has a solids content of 10.8% and a -viscosity at 25C of approximately 30 cP, as measured in a Haake Viscotester.
The use of sizing agents A - H is described by way of example in the following:
The sizing solution used for surface sizing consisted of -a solution of 5% by weight of starch (Perfectamyl A 4692, a product of the AVEBE company) and 0.25% by weight or, in some cases, 0.5% by weight of the sizing agent to be ~~
tested (expressed as active substance) in 94.75% by weight or 94.5% by weight of water.
A laboratory sizing press of the type manufactured by the Werner Mathis company of Zurich (type HF) was used for sizing. The sizing solution had a temperature of approximately 20~C in the sizing press. The paper was drawn through the sizing press at a rate of 4 metres per minute.
The surface-sized papers were dried in 45 seconds at about 100C on a drying cylinder. Before the sizing test, the papers were conditioned for 2 hours at ambient temperature.
Pieces of the paper were then preweighed, immersed for 1 `
minute in water at 20C, squeezed oncebetween filter paper under the weight of a 10 kg roll and then reweighed. The value for the absorption of water on both sides was calculated .~
-''i''7~
~J
-. ~ . ,-, :, ~ - .
~19758 in g/m2 from the difference ln weight The lower the water absorption, the better the effect o~ the tested sizing agent. A good sizing eXfect i9 shown by a water absorption of about 40 g/m2 or less.
This Example is intended to demonstrate that good sizing effects can be obtained with the described sizing agents on unsized papers o~ bleached pulps.
The raw paper used had been produced ~rom bleached sulphite pulp with the addition o~ 3 ~ of China Clay (expressed as ash) at pH 6.8 and had a weight per unit area Or 70 g/m2.
: Table 1:
Surface sizing on unsized paper of bleached ~ulp Water absorption in g/m2 with addition of Sizing agent 0.25 ~ by weight 0.5 ~ by weight of sizing~agent (based on pure active substance) to the sizing solution:
: ~ A 38.0 B 56.8 38.1 ~: C 57.7 40.0 ; D 43.9 E 44.2 F 39.9 In the absence of sizing agent, water absorption is : 87 g/m .
This Example demonstrates the ei~ectiveness o~ the described sizing agents on papers containing mechanical wood pulp. The raw paper used had been produced from 50 ~
bleached mechanical wood pulp and 50 ~ bleached sulphite Le A 18 058 _ 14 _ 1119'7~i~
p u l p W i t. ll t}~ e a d d i t, i O I~ O f I 1 ~lo () I ( ~ h ~ l y ( . ~ 1 ', ash) A t p~l 5 and ha~l a we i gil t ~)cr ulli t al`cSl 1~1 7(; ~r;/m~~
Table 2~
__ Surface sizing on unsized paper eontai~ n" mechaJ~ic~:t wood pulp Si~ing agent Water absorption i.n g/m wi,th addition of O . 25 /0 hy ~eight 0 . 5 /0 by weight of sizing agent (based on pure ac ti-ve subs tance~
to the si~;ing solution:
3!~ 0 B 68 4 37. 6 C 55 . l 34 ~ 8 D 33.3 E 34.5 F 31.0 G 31~2 H 31.0 In the absence OI sizing agen-t, water absorption is 92 . 7 g/m This Example demonstrates the favourable e~fec-t of the described siz.ing agents on papers containing cal cium carbonate ~
The raw paper used had been prod-uced from 51) /0 bl.eached pine sulphite and 50 /0 bleached beech sulphate pulp with the addition of 14 /0 precipitated ca:l ci~n carbonate ( e2~pressed as ash) at lpH 6 . 8 and had a weight per unit area of 70 g/m 0 Le A 18 058 - 15 -~975B
Table 3:
Surface sizing on unsized paper containing calcium carbonate Sizin~ agent Water absorption in g/m2 with addition of 025 ~ by weight 0.5 ~ by weight of sizing agent (based on pure active substance to the sizing solution:
A 37.0 B 53.4 31.8 C 54.5 44.5 D 32.8 E 35.7 F 32.6 G 33.5 H 34.6 In the absence of sizing agent, water absorption amounts to 77.6 g/m .
In this Example, one of the described products, sizing agent J, is compared with a cationic "sizing agent M"
which represents the prior art and which corresponds in its composition to the products described in G~En Patent Nb.
1,621,688.
The following raw papers were used:
20 Raw paper I: as described in Example 1 " II: as described in Example 3 III: bleached pulp, approximately 12 ~ oi talcum ash, 1 ~ of aluminium sulphate, unsized; approx.
80 g/m 25: " IV: bleached pulp, approximately 7 ~ China Clay ash, presized with 0.1 ~ o~ resin size and 0.5 oi aluminium sulphate; approx. 75 g/m2.
The degree of sizing against ink was determined by means o~ a Hercules Sizing Tester in accordance with the operating instructions of the~manuiacturers, Hercules Inc., Le A 18 058 - 16 -'.' ' ~'. - , - - `.: ~`''. ' `; ' `.
. .
~9758 Wilmington, Delaware, USA. The test apparatus used measures th0 period of time in seconds which is required for the remission value to fall to 75% of the remission value of paper when the test ink is applied to the paper and penetrates through it. The longer the time measured, the better the degree of sizing.
Table 4:
Comparison of one of the described products, sizing agent J, with a standard commercial-grade sizing agent M on various papers ~ -~
Paper: Sizing agent: Degree of sizing with addition of 0.125 0.175 0.25 % by weight of active substance to the solution: -.
I Comparison M79 177 352 secs.
Sizing agent J 144 344 401 secs.
II Comparison M19 69 152 secs.
Sizing agent 1 77 231 298 secs.
III Comparison M129 424 532 secs.
Sizing agent J 245 619 816 secs.
IV Comparison M42 130 304 secs.
Sizing agent J 194 237 414 secs.
It can clearly be seen that, in all the unsized and presized papers tested, the sizing effect of sizing agent J
is considerably superior to that of the standard commercial-grade sizing agent M in the three practical concentrations selected.
This Example demonstrates the suitability of the described sizing agents for use in pulp.
1 % and 2 % of sizing agent ~active substance, based on dry pulp) were added with stirring to a pulp of 50 % of birch sulphate, 30 % of pine sulphate and 20 % of spruce .. . .
., - - ; . :~ -- . : . -- , ~ ., sulphite pulp (pulp density 0.5 ~) at a pH-value of 6.9.
Sheets of paper were then immediately formed on a laboratory sheet former and dried at 100C. The paper had a weight per unit area of approximately 100 g/m2.
The sizing effect was determined by the "ink float test"
normally applied in the paper industry, i.e. by applying the papers to test ink (Pelikan 4001).
A cationic "sizing agent M", corresponding to the products described in German Patent No. 1,621,688, was again used for comparison.
Table 5:
Comparison of the described sizing agents with a standard commercial grade sizing agent M when used in pulp Sizing agent: Ink float test: no penetration of ink through paper pulp-sized with 1 ~ by weight 2 /0 by weight Sizing agent M 10 mins after 20 mins.
" A 10 mins. 20 mins.
" B 10 mins. 20 mins.
C 1 min. 2 mins.
D 5 min~. 20 mins.
" E 10 mins. 20 mins.
" G 10 mins. 20 mins.
" H 10 mins. 20 mins.
Le A 18 05~ - 18 -
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the surface sizing paper which comprises using as a sizing agent a salt of an organic or inorganic acid with a polyimide amine derived from a copolymer of maleic acid anhydride and 2,4,4-trimethyl-1-pentene with an average molecular weight of from 8000 to 500,000 and obtained therefrom by reaction in anhydrous organic medium at temperatures of from 0 to 200°C with a mixture of A) a diamine containing a tertiary and a primary amino group corresponding to the formula where R is a linear alkylene chain of 2 to 6 methylene groups and R1 and R2 represent linear C1-C4-alkyl radicals and B) ammonia or a primary monoamine from the group consisting of methylamine, ethylamine, n-propylamine, n-butylamine, n-hexylamine, cyclobexylamine, 2-ethylhexylamine and dehydroabietylamine, the molar ratio of A) and B) amounting to between 1 : 0.3 and 1 : 2.0 and at least 80% of the anhydride groups having been converted into the correspond-ing imide groups.
2. A process as claimed in claim 1, wherein the paper-sizing agent is derived from an equimolar, alternating copolymer of maleic acid anhydride and 2,4,4-trimethyl-1-pentene with an average molecular weight of from 10,000 to 60,000, of which the intrinsic viscosity amounts to between 0.08 and 0.3 d1/g (as measured in dimethyl formamide at 25°C).
3. A process as claimed in claim 1, wherein an amine mixture of 1-amino-3-dimethylaminopropane and ethylamine in a molar ratio of from 1 : 1 to 1 : 1.6 is used.
4. A process as claimed in claim 1, 2 or 3 wherein the paper-sizing agent has a degree of imidation of more than 85%.
5. A process as claimed in claim 1, wherein said organic or inorganic acid is formic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, nitric acid or sulphuric acid.
FEATHERSTONHAUGH ? CO.
OTTAWA, CANADA
PATENT AGENTS
FEATHERSTONHAUGH ? CO.
OTTAWA, CANADA
PATENT AGENTS
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772732851 DE2732851A1 (en) | 1977-07-21 | 1977-07-21 | USE OF POLYIMIDAMINE SALT AS A CATIONIC SURFACE SIZE FOR PAPER |
| DEP2732851.4 | 1977-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1119758A true CA1119758A (en) | 1982-03-16 |
Family
ID=6014437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000307675A Expired CA1119758A (en) | 1977-07-21 | 1978-07-19 | Use of polyimide amine salts as cationic surface sizing agents for paper |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0000706B1 (en) |
| JP (1) | JPS5423709A (en) |
| AT (1) | ATA522478A (en) |
| CA (1) | CA1119758A (en) |
| DE (2) | DE2732851A1 (en) |
| IT (1) | IT7850367A0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6319977B1 (en) | 1996-08-20 | 2001-11-20 | Rohm And Haas Company | Aqueous polish compositions containing acid-amine latexes |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6045642B2 (en) * | 1980-09-19 | 1985-10-11 | 電気化学工業株式会社 | Thermoplastic resin manufacturing method |
| JPS60184875A (en) * | 1984-03-05 | 1985-09-20 | Fuji Photo Film Co Ltd | Thermal recording paper |
| EP0353899B1 (en) * | 1988-07-18 | 1993-12-29 | Courtaulds Coatings (Holdings) Limited | Coating compositions |
| GB8817085D0 (en) * | 1988-07-18 | 1988-08-24 | Int Paint Plc | Coating compositions |
| AU736677B2 (en) * | 1996-08-20 | 2001-08-02 | Rohm And Haas Company | Process for preparing polymer compositions containing both acid and amine functionality |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1621693B2 (en) * | 1968-02-23 | 1975-06-19 | Bayer Ag, 5090 Leverkusen | Anionic paper sizing agents |
| DE2544948C3 (en) * | 1975-10-08 | 1978-11-16 | Akzo Gmbh, 5600 Wuppertal | Process for the production of cationic sizing agents for paper |
-
1977
- 1977-07-21 DE DE19772732851 patent/DE2732851A1/en not_active Withdrawn
-
1978
- 1978-07-12 EP EP78100381A patent/EP0000706B1/en not_active Expired
- 1978-07-12 DE DE7878100381T patent/DE2860576D1/en not_active Expired
- 1978-07-19 CA CA000307675A patent/CA1119758A/en not_active Expired
- 1978-07-19 JP JP8721478A patent/JPS5423709A/en active Pending
- 1978-07-19 IT IT7850367A patent/IT7850367A0/en unknown
- 1978-07-19 AT AT522478A patent/ATA522478A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6319977B1 (en) | 1996-08-20 | 2001-11-20 | Rohm And Haas Company | Aqueous polish compositions containing acid-amine latexes |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2732851A1 (en) | 1979-02-08 |
| JPS5423709A (en) | 1979-02-22 |
| DE2860576D1 (en) | 1981-04-23 |
| ATA522478A (en) | 1981-04-15 |
| IT7850367A0 (en) | 1978-07-19 |
| EP0000706B1 (en) | 1981-04-01 |
| EP0000706A1 (en) | 1979-02-21 |
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