EP0331047A1

EP0331047A1 - Papermaking process comprising the addition of high molecular weight poly(vinylamines) to the wet-end cellulose fiber slurry

Info

Publication number: EP0331047A1
Application number: EP89103305A
Authority: EP
Inventors: Ta-Wang Lai; Bheema Rao Vijayendran
Original assignee: Air Products and Chemicals Inc
Current assignee: Air Products and Chemicals Inc
Priority date: 1988-03-04
Filing date: 1989-02-24
Publication date: 1989-09-06
Also published as: FI890994A0; FI890994A; JPH026685A

Abstract

A high molecular weight polymer, comprising at least 10% of vinyl amine units produced by hydrolysis of a polyvinyl amide, for use as a wet-end papermaking additive to increase the dry strengh of the paper product or improve the pigment retention.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of copending application Serial No. 914,046 filed 1 October 1986, which is hereby incorporated by reference.

TECHNICAL FIELD

The invention relates to the use of high molecular weight poly(vinylamines) in the papermaking process.

BACKGROUND OF THE INVENTION

Water soluble polymers such as poly(N-vinylamides), frequently require high molecular weight to develop satisfactory properties for high performance applications. Low to medium molecular weight poly(N-vinylformamide) and poly(N-vinylacetamide) have been prepared by conventional solution polymerization in water and alcohols using oil-soluble and water-soluble initiators. However, poly(N-vinylamides) of high molecular weight are difficult to produce by conventional solution polymerization in that the polymer product obtained under useful conditions is a gel which is difficult to handle. In addition, problems with high solution viscosity and poor heat transfer make such synthesis impractical on a commercial scale.
Nonetheless, it was believed by the present inventors that the applications performance of poly(vinylamides] and poly(vinylamines) could be enhanced by the preparation and use of homopolymers of very high molecular weight (>10⁶).
U.S. 3,597,314 discloses that dewatering of aqueous cellulose fiber suspension in the formation of paper is improved by adding to the suspension from 0.05 to 4% of a water-soluble polymer consisting essentially of units derived from N-vinyl-N-methylformamide having 60-100% of the formic acid radicals of the polymer split off by acid hydrolysis.
U.S. 4,623,699 discloses linear, basic polymer powders which contain units of the formula -CH₂-CH(NH₂)- and have a Fikentscher K value from 10 to 200 are prepared by eliminating the formyl groups from N-vinylformamide polymer powders with a gaseous hydrogen halide in the presence of not more than 5% by weight, based on the polymer used, of water. Polymers which contain 10-90 mole% of units of vinylamine and 10-90 mole% of units of vinyl formamide as well as poly(vinylamine) are said to be used as flocculents for waste waters and sludges and as retention agents, drainage aids and flocculents in papermaking.
U.S. 4,500,437 discloses acrylamide copolymers and terpolymers containing N-vinylformamide and N-vinylacetamide prepared by inverse emulsion polymerization in Examples 67-70 with the polymers of Examples 68 and 70 having a molecular weight below 100,000; i.e <10⁵. Example 20 shows the preparation of poly(vinylformamide) by solution polymerization.
U.S. 4,421,602 discloses linear basic polymers containing from 90 to 10 mole% of copolymerized vinylamine units and from 10 to 90 mole% of copolymerized N-vinylformamide units. This patent teaches that the polymers can be prepared by solution polymerization in water, a water-soluble solvent or a mixture of water and a water-soluble solvent and actually shows such solution polymerization in the examples. It is suggested that the polymerization can also be carried out as a water-in-oil emulsion polymerization in a water-immiscible solvent, but there are no examples of such polymerization.
U.S. 4,018,826 discloses the preparation of poly(vinylamine) salts of mineral acids by polymerizing vinylacetamide with a free radical polymerization catalyst, and hydrolyzing the poly[vinylacetamide) to the desired amine salts by contacting the poly(vinylacetamide) with an aqueous solution of the corresponding mineral acid. Poly(vinylamine) product of about 3,000 to about 700,000 molecular weight (4,000 to about 1,000,000 for the salt product) is suggested.
U.S. 3,558,581 discloses homo- and copolymers of N-vinyl-N-methylamine by hydrolysis of the corresponding polymers of N-vinyl-N-methylformamide with mineral acids.
GB 2,152,929 is directed to a process for producing N-substituted formamides for use in producing N-vinylformamide by thermally decompos ing N-(alpha-alkoxyethyl)formamide in the gas phase. It is suggested that the N-vinylformamide can be bulk polymerized, solution polymerized using an aqueous solution or an organic solution, or emulsion polymerized singly or together with a monomer used conventionally for producing water-soluble polymers suitable for making flocculants, in the presence of a polymerization initiator of azo compounds. The thus obtained poly(vinylformamide) is hydrolyzed under acidic or basic conditions to obtain a cationic polymer of poly(vinylamines).
D. J. Dawson, et al., "Poly(vinylamine hydrochloride). Synthesis and Utilization for the Preparation of Water-Soluble Polymeric Dyes," J. Am. Chem. Soc., 98:19, 5996 (1976) discloses the preparation of N-vinylacetamide and its polymerization in solution followed by acid hydrolysis to poly(N-vinylamine hydrochloride).
Representative of the numerous prior art references relating to water-in-oil emulsion polymerization of water-soluble monomers are the following patents: U.S. 2,982,749; 3,278,506; 3,284,393; 3,957,739; 3,975,341; 4,078,133; and 4,312,969.
R. H. Summerville, et al., "Synthesis of N-vinyl Acetamide and Preparation of Some Polymers and Copolymers," Polym. Reprints, 24, 12 (1983) discloses that the inverse emulsion polymerization of N-vinylacetamide initiated by sodium persulfate in water and cyclohexane using Igepal surfactants was tried without success.
U.S. 4,217,214 discloses that polyvinylamine hydrochloride having a molecular weight of about 5 x l0⁵ or greater has been found to be particularly effective as a flocculating agent in wastewater systems. The examples disclose the use of a poly(vinylamine) hydrochloride having a molecular weight of 2 x 10⁶ and state that the poly(vinylamine) hydrochloride used is prepared as described in U.S. 4,018,826.
JP 61/141712 discloses a method for producing N-vinylcarboxylic acid amide polymers by a procedure in which an aqueous solution of N-vinylcarboxylic acid amide is dispersed in a hydrocarbon-type dispersing medium using an oil-soluble polymer dispersion stabilizer followed by radical polymerization.

SUMMARY OF THE INVENTION

According to the present invention, very high molecular weight poly(N-vinylamides) can be prepared by an inverse emulsion polymerization process. The present invention provides an inverse homopolymer emulsion consisting essentially of 10-70 wt% of an aqueous solution containing 10-90 wt% of a homopolymer of an N-vinylamide of the formula
wherein R and R¹ represent hydrogen or a C₁-C₄ alkyl group, colloidally dispersed in a hydrocarbon liquid which is a C₅-C₁₀ alkane and, in addition, toluene and xylene when R=alkyl, a xylene compound, the homopolymer being at least 10⁶ average molecular weight and the emulsion possessing a viscosity less than 10 cps at 15% solids, 60 rpm Brookfield (7.9 sec⁻¹) and 20°C.
The method for preparing the inverse, or water-in-oil, emulsion involves colloidally dispersing an aqueous solution containing 10-90 wt% water-soluble N-vinylamide of the above formula in the hydrocarbon liquid using a surfactant having an HLB value from 4 to 9, the weight ratio of monomer-containing aqueous solution to hydrocarbon liquid being preferably in the range from 1:2 to 2:1, and polymerizing the monomer using an azo-type free radical initiator.
The resultant very high molecular weight polymer emulsion has a low viscosity ranging from 2 to less than 10 cps at 15% solids, 60 rpm Brookfield and 20°C, thus eliminating problems of solution viscosity which arise when the polymer is prepared by a solution polymerization process. In addition, the low viscosity homopolymer emulsion is easy to handle and can be used directly.
One such use of the vinylamide homopolymer emulsions is in the preparation of vinylamine homopolymers of at least a 10⁶ average molecular weight by acid or base catalyzed hydrolysis of the homopolymer, preferably as the emulsion. The use of the mineral acid in the hydrolysis step or in acidifying the base hydrolysis product provides the poly(vinylamine) as the salt of such acid.
The very high molecular weight derived poly(vinylamines) have application in the field of papermaking.
The present invention also provides an increase in retention, drainage rate and flocculation in a papermaking process comprising the deposition of a pulp stock, or cellulose fibers, to form a nonwoven sheet by adding to the pulp stock poly(vinylamines) according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

Poly(N-vinylamides) of molecular weight at least 10⁶, preferably 3 x 10⁶ to 15 x 10⁶, are prepared via an inverse emulsion polymerization process by reacting the following composition under an inert atmosphere:

1. water-soluble N-vinylamide monomer,
2. water,
3. hydrocarbon liquid,
4. water-in-oil emulsifying agent, and
5. a nitrogen-containing free radical initiator.

The aqueous solution comprising the first two components contains 10 to 90 wt%, preferably 50 to 70 wt%, of a water-soluble N-vinylamide of the formula
where R and R¹ represent hydrogen or an alkyl group having 1-4, preferably 1-2, carbon atoms, especially a methyl group. The weight ratio of monomer-containing aqueous solution to hydrocarbon liquid may be varied widely depending upon the monomer used, but preferably is about 1:2 to 2:1.
The suitable hydrocarbon liquids for use in the invention are immiscible with water and do not significantly dissolve the monomers in the presence of water. Such hydrocarbon liquids are exemplified by acyclic and cyclic C₅-C₁₀ alkanes such as hexane, octane, decane, and decahydronaphthalene (decalin) and, in addition, certain aromatic hydrocarbons for N-vinylacetamides and the aromatic hydrocarbons toluene and xylene. Contemplated as the functional equivalent of toluene and xylene when R is an alkyl group in the monomer formula are ethylbenzene and tetrahydronaphthalene (tetralin). The preferred hydrocarbon liquids are the C₅-C₁₀ acyclic alkanes.
The stabilizing system comprises suitable emulsifying agents, or surfactants, having a hydrophilic-lipophilic balance (HLB) value from 4 to 9, preferably 4 to 7.5, and include sorbitan fatty acid esters such as sorbitan monostearate, oleate, laurate or palmitate; polyoxyethylene-sorbitan fatty acid esters, i.e. reaction products of one mole of the aforementioned sorbitan fatty acid esters with from 4 to 40 moles of ethylene oxide; polyoxyethylene sorbitol esters of fatty acids; and mixtures thereof. The preferable quantity of surfactant is 5 to 20 wt% based on the monomer-containing aqueous solution.
The free radical initiator should be one of the azo compounds well known in the polymerization art such as 2,2′-azobis(isobutyronitrile); 2,2′azobis(2-amidinopropane) hydrochloride; 4,4′-azobis(4′-cyanopentanoic acid) and the like. Persulfates and hydrogen peroxide have been found not to be suitable in practicing the invention. Redox catalyst systems may also be used comprising the azo initiators with a reducing agent typically used in the art. The amount of free radical initiator can be varied widely depending upon reaction temperatures, rate of polymerization, degree of polymerization to be obtained, but preferably is in the range of 0.001 to 0.5 mole% of the monomer used.
The polymerization is usually carried out under an inert atmosphere, preferably under nitrogen. The reaction temperature is preferably in the range of 40-60°C. A high temperature, i.e. >60°C, may cause side reactions unfavorable to the polymer such as crosslinking or chain transfer. A lower temperature may be impractical because of long reaction times.
The homopolymer product can be isolated from the emulsion by adding a flocculating agent and filtering. The precipitated product is then washed and dried. Generally, a polar organic solvent which is a good solvent for the surfactant but a poor solvent for the polymer, e.g. acetone, is used to aggregate the polymer. The precipitated polymer is filtered and washed to remove the surfactant. The dried and purified polymer of very high molecular weight is in the form of a fine powder and is water soluble.
The vinylamide homopolymer products are hydrolyzed to vinylamine homopolymers of at least 10⁶ average molecular weight in the presence of acids or bases. More desirably, vinylamine homopolymers of 1.8 x 10⁶ to 9 x 10⁶ molecular weight or more are obtained. The vinylamine polymers suitable for use as wet-end additives in the papermaking process are at least 10% hydrolyzed and desirably greater than about 50% hydrolyzed, preferably greater than about 90%, to about 99+% hydrolyzed.
Suitable acids for the hydrolysis include mineral acids such as hydrochloric, hydrobromic, sulfuric, phosphoric and perchloric acid; and organic acids such as trifluoroacetic acids and methanesulfonic acid. The bases which can be employed include alkali and alkaline earth hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide; and quaternary ammonium hydroxides such as tetramethyl ammonium hydroxide. The quantity of the acid or base required may vary widely, depending upon the degree of hydrolysis desired and reaction conditions. Approximately, 1 to 3 equivalents of the acid or base per equivalent of the polymer is preferred to achieve essentially complete hydrolysis.
The hydrolysis can be performed in various solvents, including water; liquid ammonia; alcohols such as methanol, ethanol, isopropanol, and t-butanol; amines such as methylamine, dimethylamine ethylamine and the like; and hydroxy amines such as ethanolamine. However, it is much preferred to simply add the acid or base in water to the water-in-oil emulsion.
The temperature of the hydrolysis may range from 20 to 200°C depending upon the type of polymer and hydrolysis employed. Generally, hydrolysis proceeds more rapidly for poly(N-vinylformamide) than for poly(N-vinylacetamide). Thus, hydrolysis of poly(N-vinylformamide) can be carried on under milder conditions, i.e. at lower temperatures and shorter reaction times than for poly(N-vinylacetamide). The preferable temperature range of a base hydrolysis is 70 to 100°C which is lower than that of acid or base hydrolysis of N-vinylacetamide in the range of 110 to 200°C.
The hydrolyzed polymer products thus obtained comprise the repeating free amino-containing units of the formula
in the case of base hydrolysis, and amino-containing units of the formula
in the case of acid hydrolysis, where X⁻ represents the anion corresponding to the acid employed in the hydrolysis.
Poly(vinylamine) is preferably isolated in the salt form to prevent adsorption of atmospheric carbon dioxide. The polymer salt is isolated by acidifying the hydrolysis mixture to cause the polymer to precipitate. The precipitated polymer generally is a gum, but a fibrous material can be obtained after redissolving, followed by reprecipitation in methanol.
The products of this invention are high molecular weight poly(N-vinylamides), especially poly(N-vinylformamide) of 3-15 x 10⁶ mol wt and poly(N-vinylacetamide) of 1.3-5 x 10⁶ mol wt, and the derived poly(vinylamine) and poly(vinylamine) salts.
These polymeric materials may also contain up to 25 wt% copolymerizable monomers such as, for example, acrylamide, N-vinyl-pyrrolidone, sodium vinyl sulfonate and acrylamidomethylpropane sulfonic acid (sodium salt), provided the polymer maintains sufficient water solubility.
With regard to the papermaking process, such process involves an aqueous cellulose fiber (wood pulp) suspension, which may contain one or more rosin size and mineral constituents (fillers) depending on the product desired, being deposited and drained on a continuously moving wire cloth. The free water passes and drops off the cellulose fiber web which undergoes further processing to yield the desired paper product. The addition of 0.05 to 0.5 wt%, preferably 0.1 to 0.2 wt%, vinylamine polymer, based on fiber, to the aqueous cellulose fiber slurry (wet-end) provides for an increase in the dry strength of the paper product and an increase in the retention of titanium dioxide in those papermaking processes that use TiO₂.

EXAMPLE 1

This Example shows a preparation of a very high molecular weight poly(N-vinylformamide) by inverse emulsion polymerization.
Sorbitan monostearate (SPAN 60 surfactant, HLB 4.7, 2.5g) was dissolved in octane (90g) and the resulting solution was transferred to a reaction kettle. The reactor was purged with nitrogen and kept in a nitrogen atmosphere throughout the polymerization. The N-vinylformamide solution (15g in 30g of water) was degassed and added to the reactor at the rate of 2.5 ml/min with vigorous agitation. (The N-vinylformamide was purified by vacuum distillation at 70°C, 1 torr, prior to use.) While the reaction mixture was heated to 50°C, 2,2′-azobis(2,4-dimethyl pentanitrile) (Vazo 52 initiator, 0.05g) was charged. After 3 hours at 50°C with agitation, a stable polymeric emulsion was produced having a viscosity of 3 cps. The solid polymer product was recovered by breaking the emulsion by the addition of acetone. The isolated N-vinylformamide homopolymer had a molecular weight of 6.7 x 10⁶ as measured by light scattering and a viscosity of 21,000 cps as a 5% aqueous solution.

EXAMPLE 2

The vinylformamide homopolymer (10g) of Example 1 was dissolved in water (990g) and then mixed with 50% aqueous sodium hydroxide (11.3g). The resulting mixture was heated for 8 hours at 80°C under a nitrogen atmosphere. To the reaction mixture was added concentrated hydrochloric acid until the polymer precipitated. The acid solution was decanted. The precipitated polymer was redissolved in water and reprecipitated with methanol. The vinylamine homopolymer hydrochloride salt had a viscosity of 400 cps at 1% aqueous solution.

EXAMPLE 3

This Example shows the preparation of a very high molecular weight poly(N-vinylacetamide) by inverse emulsion polymerization.
The N-vinylacetamide was prepared according to the method taught in U.S. Patent 4,018,826. The N-vinylacetamide was purified as follows: The crude N-vinylacetamide (1 kg) was flash distilled at 70-74°C, 1 torr. Approximately two-thirds of the material was distilled to give a 70:30 N-vinylacetamide/acetamide mixture. This mixture (100g) and toluene (600g) were placed in a 1000 ml beaker and the resulting mixture was stirred well. The yellow toluene solution was decanted from insoluble solids which were washed twice with 50g of fresh toluene. The toluene solutions were combined and washed with 25g of brine. The yellow brine solution was discarded. The toluene solution was then extracted four times with 130 ml of water. The aqueous solution was back extracted with 25 ml of methylene chloride. The methylene chloride solution was discarded. The aqueous solution was saturated with sodium chloride and extracted four times with 330 ml methylene chloride. After removing the methylene chloride under reduced pressure, 42g of pure N-vinylacetamide (60% recovery) was obtained.
A mixture of N-vinylacetamide (15g), water (45g), xylene (90g), and SPAN 60 surfactant (4g) was polymerized in the same manner as described in Example 1, using 2,2′-azobis(2-methylpropionitrile) AIBN (0.08g) as an initiator. The N-vinylacetamide homopolymer was precipitated by addition of acetone, and had a molecular weight of 1.5 x 10⁶, as determined by gel permeation chromatography.

EXAMPLE 4

The N-vinylacetamide homopolymer of Example 3 (10 g) was dissolved in water and mixed with concentrated hydrochloric acid (2 mole equivalents). The resulting mixture was heated to reflux (about 110°C) for 48 hours. To the reaction mixture was added concentrated hydrochloric acid until the polymer precipitated. The acid solution was decanted. The precipitated polymer was redissolved in water and reprecipitated with methanol yielding 8.8g of product having a viscosity of 324 cps as a 1 % aqueous solution.

EXAMPLES 5-9

N-vinylformamide (NVF) was polymerized in the same manner as described in Example 1. The data regarding the polymerization recipes and the resulting emulsions are set forth in Tables 1 and 2, respectively.

TABLE 1

EXAMPLE	NVF(g)	WATER(g)	HYDROCARBON(g)		SPAN 60(g)	VAZO 52(g)	ADDITIVE(g)
5	15	30	Octane	55	2.5	0.05	---
6	15	30	Octane	55	2.5	0.05	0.25 Vinol 125
7	15	10	Octane	75	2.5	0.05	---
8	15	30	Hexane	90	2.5	0.05	---
9	15	30	Hexane	90	2.5	0.05	0.25 Poly(vinylamine)

TABLE 2

EXAMPLE	EMULSION VISCOSITY (cps)	HOMOPOLYMER MOLECULAR WEIGHT
5	4	7 x 10⁶
6	4	7 x 10⁶
7	4	6 x 10⁶
8	4	6 x 10⁶
9	4	6 x 10⁶

EXAMPLE 10

In this example the inverse emulsion polymerization of N-vinylformamide according to Example 1 was attempted using toluene, xylene and kerosene individually as the hydrocarbon liquid phase. In each instance a high molecular weight N-vinylformamide polymer was obtained, but the emulsions were unstable and broke.

EXAMPLE 11

This Example demonstrates the use of the vinylamine homopolymer as a dry strength additive in paper making application.
Paper chromatography grade stock of uniform size was immersed in water, metered through squeeze rolls and weighed. Water pick-up was calculated and determined consistent from sheet to sheet. The weight of polymer required per unit water volume to impart 0.5% polymer pick-up on sheet weight (dry/dry) was determined.
The low molecular weight (80M) vinylamine homopolymer and polyvinyl alcohol were applied at 0.75%. The high molecular weight (7MM) vinylamine homopolymer which was an extremely high 3200 cps in viscosity was diluted to 0.188% solids and assumed to be 0.125%, the add-on level of the others. The polymers were adjusted to pH 4.5 prior to sheet saturation. TABLE 3

Polymer Saturant Instron Tensile lb/in Mullen Burst lb/in² Tear CMD

Blank 11.5 0.6 71

VAm (80 M) 13.5 2.5 77

VAm (7 MM)^a 14.5 3.1 89

VINOL 107 PVOH^b (60 M) 12.5 2.0 80

^a 0.125% add-on compared to 0.5% for the others.

^b Polyvinyl alcohol marketed by Air Products and Chemicals, Inc.
It can be seen that the very high molecular weight vinylamine homopolymer was an effective dry strength additive in papermaking at 1/4 the dosage compared to the low molecular weight vinylamine homopolymer.

EXAMPLE 12

This Example shows the retention characteristics of the vinylamine homopolymer in papermaking.
Immediately prior to hand sheet preparations, softwood and hardwood bleached kraft pulps were each suspended at 1.5% consistency in deionized water. The pulps were then blended 1:1 by weight and an amount equivalent to 30g (oven dry basis) was utilized in preparing each set of hand sheets. Ten percent of anatase TiO₂ based on fiber weight was added followed by 5 minutes of stirring. (The TiO₂ was predispersed at 10% solids in deionized water). Sufficient pulp to form a 2.5g hand sheet was removed and treated with polymer followed by 30 seconds of moderate stirring. The treated fiber suspension was then added to a Noble and Wood sheet mold containing sufficient deionized water to provide a forming consistency of 0.04%. Hand sheets formed from the fiber suspensions were pressed 5 minutes at 50 psig between blotter stock and then drum dried 7 minutes at 220°F in contact with one blotter.

Following this procedure the polymers were added to the fiber suspension at 0.5% consistency at addition levels of 0, 0.01, 0.05, 0.1, 0.2 and 1% based on fiber. The pH was maintained at 5. Hand sheets prepared in the manner described were conditioned at 50% RH and 73°F and test for filler retention using TAPPI standard method.

TABLE 4

Polymer	% TiO₂ Retention
VAm (7 MM)	93.1
VAm (80 M)	83.3
Hercules 834 Heterofloc High Mol. Wt./High Charge Density, PAM (2-4 MM)	85.6

Allied Colloid DSR 1256 Low Mol. Wt./Low Charge Density, PAM (<1 MM)	54.0
PAM = Polyacrylamide

It can be seen that the 7MM molecular weight poly(vinylamine) demonstrated a superior TiO₂ retention at 0.1-0.2% addition level to wood pulp.

STATEMENT OF INDUSTRIAL APPLICATION

The present invention provides very high molecular weight poly(N-vinylamides) by inverse emulsion polymerization and derived poly(vinyl amines) having application in the wet-end of the papermaking process.

Claims

1. In a papermaking process in which cellulose fiber is deposited from an aqueous slurry containing polymer additives for strengthening the paper product, the improvement which comprises the addition of 0.05 to 0.5 wt%, based on fiber, of a poly(vinylamide) of at least 10⁶ average molecular weight and at least 10% hydrolyzed to vinylamine units.

2. The process of Claim 1 in which the poly(vinylamine) has a 1.3-15x10⁶ average molecular weight.

3. The process of Claim 1 in which the poly(vinylamide) has a 1.8 -9 x 10⁶ average molecular weight.

4. The process of Claim 1 in which the poly(vinylamide) is greater than about 50% hydrolyzed to vinylamine units.

5. The process of Claim 3 in which the poly(vinylamide) is greater than about 90% hydrolyzed to vinylamine units.

6. The process of Claim 1 in which the poly(vinylamide) is about 7 x 10⁶ average molecular weight.

7. The process of Claim 1 in which the poly(vinylamide) is about 99+% hydrolyzed to vinylamine units.

8. The process of Claim 5 which comprises the addition of 0.1 to 0.2 wt% of the poly(vinylamide).

9. In a papermaking process in which cellulose fiber is deposited from an aqueous slurry containing polymer additives for increasing the retention of TiO₂ in the paper product, the improvement which comprises the addition of 0.05 to 0.5 wt%, based on fiber, of a poly(vinylamide) of at least 10⁶ average molecular weight and at least 10% hydrolyzed to vinylamine units.

10.The process of Claim 9 in which the poly(vinylamide) has a 1.3-15 x 10⁶ average molecular weight.

11. The process of Claim 9 in which the poly(vinylamide) is greater than about 50% hydrolyzed to vinylamine units.

12. The process of Claim 10 in which the poly(vinylamide) is greater than about 90% hydrolyzed to vinylamine units.

13. The process of Claim 9 in which the poly(vinylamide) is about 7 x 10⁶ average molecular weight.

14. The process of Claim 9 in which the poly(vinylamide) is about 99+% hydrolyzed to vinylamine units.

15. The process of Claim 12 which comprises the addition of 0.1 to 0.2 wt% of the poly(vinylamide).