AU537112B2 - Hydrolysed styrene-maleic anhydride copolymers - Google Patents
Hydrolysed styrene-maleic anhydride copolymersInfo
- Publication number
- AU537112B2 AU537112B2 AU62551/80A AU6255180A AU537112B2 AU 537112 B2 AU537112 B2 AU 537112B2 AU 62551/80 A AU62551/80 A AU 62551/80A AU 6255180 A AU6255180 A AU 6255180A AU 537112 B2 AU537112 B2 AU 537112B2
- Authority
- AU
- Australia
- Prior art keywords
- copolymer
- dispersion
- styrene
- maleic anhydride
- solution
- 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.)
- Ceased
Links
Classifications
-
- 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
- C08F8/44—Preparation of metal salts or ammonium salts
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Medicinal Preparation (AREA)
Description
-x
.(CONVENTIQN -By oni
citms
0 y~i)
Here insert (in lull) Name or Nfames of we ,Applicant or a SAPPllCanta, o mfollowed by Address
(2 ier o fli3osflf j9ifd''~ Ii
insert Titlre hereby apply f of Invention.
-THEREOF. millIfl! tos 0 (30 e e i s r
which is des4 illliI'l M Hereinsert Convention al 2 Z1111 -411 0 11111 ofNaeofbai
00 aicdteo
for a patent dotes on 22nd
'4 Melbourne Our *~444~~ "-4 5W Queen 4
Signa- ture of Applicant (s) Selo Seorp Company and Signatures of its OffIcers aa prewribed by its Articles of Aasoclaticn. U -4 s
Form COMMONWEALTH OF AUSTRALIA
PATENTS ACT 1952-69
The inv~l COMPLETE SPECIFICATION persion a (ORIGINAL) process for t Prepar'a
Nr
'(00O1VENTION. -By one or 4pro and/n C
~COMMONWEAL
Patents Act 1,
CONVNTON VPULCAT\*1 A
Here insert(in -0 HOECHST AKTIENGESELLSCHAFT.. full) NqameW or Names of e S 1 :Ppll or tolloved by n5.,uingstrasse. D5230..Fra-nk-f.urt/Main. Address
F-jeeral Republis. Germ any AUT&LA
()Zeehereby apply for the grant of a Patent for an inverition entitled:[22
UEOUIS. 41LUT.ION OR.DEPER.I.N. QFTv TR~E~LI ANHYDRI.DE C.OP.OLYMER AIIjD.. PROCESS FOR THEPR AATO
0 THEREOF
nurnbsr which is described in the accompanying complete specification. This application is a of basic 49 6 ~'isInS Convention application and is based on the application numbered(3
I Here Insert
1;I- Name of basic 4 Country o. forTe~r l. contI and fra patent or. similar protection made in FdrlREpublic..o.f Germn dateson 22nd September 1979
AT LOD7GED ])~~bUrne address for service is Messrs. Edwd. Waters Sons, Patent Attorneys, Queen Street, Melbourne, Victoria, Australia.
-DATED 8th da of..
Signa- HS T. GSELLSCHAFT ture of Applicant (s) SIIo Soar~ Company and Signatures of Its Omoocrs as pre.y'rIIbed by Its Articles of Assorts (ion. Louis C Gebhardt
-2 HOE Y.9/F 253
The invention relates to an aqueous solution or dis- persion o' a styrene/maleic anhydride copolymer and a process for the preparation thereof. Preparation of' copolymers of maleic anhydride with
Form 7
COMMONWEALTH OF AUSTRALIA Patents Act 1952
In support of the Convention application made under Part XVI.. of the Patents Act 1952 by HOECHST AKTIENGESELLSCHAFT of Br~ningstrasse, D-6230 Frankfur't/Main 80, Federal Republic of Germany for a patent for an inventicn entitled: "AQUEOUS SOLUTION OR DISPERSION OF A STYRENE/MALEIC ANHYDRIDE COPOLYMER AND PRO4CESS FOR THE PREPARATION THEREOF" WJohann-Heinrich Reuter, 4 Bodenheimer Stral~e, D-65oo Mainz Martin von Fdrster, 8 Wiesenstra~e, D-05240 K.6nigstein/Taunus; 4#tfl*k Federal Republic of Germany do solemnly and sincerely declare as follows: 0
4 Ga 0 1. We are authorized by HOECHST AKTIENGESELLSCHAFT the applicant 44 4 for the patent to make this declaration on ifr: oehaif,I 04 4 00 #4
*0 2. The basic application as dofined by Section 141 of the Act vas made in the Federal Republic of Germany under No. P 29 38 429. 0 on September 22, 1979 by HOECHST AKTIENGESELLSCHAFT
4400 3. Ernst N6lken, 16a Dachbergstra~e, D-6232 Bad Soden amn Taunus 44*0 Federal Republic of Germany S 4 C t.W
is/mthe actual inventor(g of the invention and the facts upon which HOECHST AKTIENGESELLSCHAFT
*4 4. is entitled to make the application are as follows:
*44 4. The said HOECHST AKTIENGESELLSCHAFT
Is the assignee of the said Ernst Ndlken
4. The basic application referred to in paragraph 2 of this Declaration was the first application made in a Convention country In respect of the invention the buoject of the application. DECLARED at Frankfurt/Main, Federal Republic of Germany this 27th day of August 1980
To the Com'issi~ner of Patents Hoechst Aktongselst
o~ristAuthorized sigriatori (ppa.Reuter) (i.V.von Ftirster) PAT 510
anhydride, wherein the molar ratio of styrene to maleic anhydride is in the range of from 1.5:1 to 6:1, Lhe molecul- ar weight is from 500 to 80,000, 1 to 60 percent of the carboxyl groups of the copolvmer are neutralized. and the
(12) AUSTRALIAN PATENT ABRIDGMENT (19) AU (11) AIJ-B-62551/80
'4 HYDROLYSED STYRENE-MALEIC ANH'iDRIDE COPOLYMER (71) HOECHST AKTIENGESELLSCHAFT (21) 62551/80 537112 (22 9.-9 (24) 22.9.79 (31) 2938429 (32) 22.9.79 (33) DE (43) 9.4.81 (a4) 7.6.84 (5.1)3 C08F 8/12 C08F 8/44 C08F 212/08 C08F 2/20 C08F 118/08 (72) ERNST NOLKEN (74) WM (56) 14441/70 413609 CO8F, C01G (09.4.33) 11827/70 444421 C08F, (09.4.33) (57) It is the object of the invention to provide an aque- ous solution or dispersion of a maleic an;,idride cooolymer which solution or dis-)ersion: does not have an alkaline reaction and is suitable as emulsifi-er solution or emulsi- ~ier dispersion 'or plastics dispersions.
1. Aqueous solution or dispersion of a hydrolyzed copoly- mer of styrene and maleic anhydride wherein the molar ratio of styrene to mrale 4 c anhydride is in the rarnge of from 1.5:1 to 6:1, the molecular weight is from 500 to 80,000, 1 to 60 percent of the carboxyl groups of the copolymer are neutralized, and the pH- of the solu ion or dispersion is below 7.
ND 20
116±561/21
Fofr COMIMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 The inve COMPLETE SPECIFICATION persion o' a (ORIGINAL) process for t Preparat vinyl compoun 6255180 (see for exan Class I nt.. Class Application Nun ler: copolymers ar Lodged: because their tive colloid, *090009 10 mation. 'Qompl-,ce. 'pecification Lodged Furthern Accepted: 0 and maleic an '.Published: vs ukumnl contains h r-rien1T Cs fl2W&_ tmd- maleic anhydr Svetkm 49. weight of fro 0 0 15 80 to 300'C Related Art: I-l s orrect tor printan, These copolym I I containing cc aqueous alkal 900*
emulsion pol- Name of Applicant: HOECHST AKTIENGESELLSCHAFT 0 9* 20 It is al *0 copolymers ha ~t0S a 9.
45 Bruningstrasse, D-6230 Frankfurt/Main 80, 00 0 dride of fron Address of Applicant: Federal Republic of Germany 1,600 to sis of starc 0-So. 9 40
SA&~ual Inventor: ERNST NOLKF.N *9 0 25 lymers are nc #0004 0 0 in an ar-)mati cal-forming a EDWD. WATERS SONS, Address for Service: 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000. to 300'C. Af droxide until Complete Specification for the invention entitled: 30 dissolved in AQUEOUS SOLUTION OR DISPERSION OF A STYRENE/MALEIC It is t ANHYDRIDE COPOLYMER AND PROCESS FOR THE PREPARATION THERBDF ous solution which solutic reaction and The following statement is a full description of this invention, including the best method of performing it known to :-US 35 fier dispersi _V1 The invE persion of a
THE CLAIMS DE1
1. Aqueous s
-2 HOE 79/F 253
A The invention relates to an aqueous solution or dis- persion o a styrene/maleic anhydride copolymer and a process for the preparation thereof. Preparation of copolymers of maleic anhydride with vinyl compounds such as styrene is known fr a long time (see for example Ind.Eng.Chem. 41 (1949), p. 1509). These copolymers are dissolved in water with addition of alkali, because their action as pigment dispersing agent, protec- tive colloid, thickener or sizing agent requires salt for- mation. Furthermore, there are described copolymers of styrene and maleic anhydride having a molar ratio of styrene to maleic anhydride of from 1:1 to 4:1, an average molecular weight of from 400 to 100,000, and a melting point of from 80 to 300 0 C (see for example U.S. Patent No. 3,444,151). These copolymers are reacted with amines to yield nitrogen- containing copolymers being nearly insoluble in water or aqueous alkaline media; they are used as emulsifiers in the emulsion polymerization of vinyl monomers. 20 It is also disclosed to use styrene/maleic anhydride copolymers having a molar ratio of styre:ne to maleic anhy- dride of from 1:1 to 3:1 and a molecular weight of from 1,600 to 50,000 for the manufacture of adhesives on the ba- sis of starch (see U.S. Patent No. 3,939,108). These copo- lymers are normally manufactured by solution polymerization in an aromatic hydrocarbon, in the presence of a free radi- cal-forming agent as catalyst, at a temperature of from to 300°C. After addition of ammonia or alkali metal hy- droxide until a pH of 8 to 11 is adjusted, they can be dissolved in water under heat. It is the object of the invention to provide an aque- ous solution or dispersion of a maleic anhydride copolymer which solution or dispersion does not have an alkaline reaction and is suitable as emulsifier solution or emulsi- fier dispersion for plastics dispersions. _The invention relates to an aqueous solution or dis- persion of a hydrolyzed copolymer of styrene and maleic
1. Aqueous solution or dispersion of a hydrolyzed copoly- anhydride, wherein the molar ratio of styrene to maleic anhydride is in the range of from 1.5:1 to 6:1, che miolecul- ar weight is from 500 to 80,000, 1 to 60 percent of the carboxyl groups of the copolymer are neutralized, and the pH of the solution or dispersion is below 7. The invention relates furthermore to a proce.ss for the preparation of an aqueous solution or dispersion of a hydrolyzed copolymer of styrene and maleic anhydride by hydrolysis of a styrene/maleic anhydride co)o lymer and partial neutralization with an inorganic neutralizing agent, which comprises heating a copolymner having a-molar ratio of styrene to maleic anhydride of from 1.5:1 to 6:1 and a 04
4* molecular weight of from 500 co 80,000 to a temperature of 0 from 75 to 2500C in the presence of water and in the pre- sence of such an amount of ammonia, an alkali metal hydrox- ide or alkaline earth metal hydroxide, or zinc oxide that is sufficient to neutralize 1 to 60 percent of the carboxyl groups of the copolymer. Moreover, the invention provides the use of the cited solution or dispersion as stabilizer solution or dis- 4 persion for aqueous dispersions, and for the dispersion poly- o 44 merization of vinyl compounds. 4 The styrene/maleic anhydride copolymer used in accordance with the invention has a molecular weight (numer- ical average) of from 500 to 80,000 preferably 800 to- 30,000. The molar ratio of styrene to maleic anhydride is from 1.5:1 to 6:1, preferably 1.6:1 to 4:1. In accordance with the invention, the styrene/ maleic anhydride copolymer is heated to a temperature of from 75 to 2500C, preferably 85 to 1800 C, in the presence of water and of an inorganic neutralizing agent, and hydrolyzed. The free carboxyl groups of the copolymer so formed are thus neutralized in a percentage of from 1to preferably 6 to
-16- HOE 79/F 253
oxide that is Sufficient to neutralize 1 to 60 percent of the carboxyl groups of the copolymer.
6. The process of claim 5. whinh nrmri- r 'C
4 HOE 79/F 253
In this alkaline treatment of the copolymer, its concentra- tion is from 5 to 50, preferably 10 to 30, by weight (re- lative to the total amount of water and copolymer). Depend- ing on the concentration and composition of the copolymer and the temperature chosen, this treatment takes from 5 mi- nutes to 5 hours, preferably 10 to 200 minutes. Large sty- rene amounts in the copolymer, high copolymer concentra- tion and low treating temperature require genera-ly a pro- longed treatment time; that is, the treatment time can be influenced by varying the above parameters. It is recom- mended to operate under inert gas, for example nitrogen. ate The styrene/maleic anhydride copolymer may contain additionally one or inore further comonomers in an amount of up to 20 mol (relative to the total monomer amount), o 0 0 15 incorporated by polymerization. Suitable are olefinically 040'
unsaturated compounds such as vinyl esters, vinyl ethers, acrylic esters, or unsaturated carboxylic acids such as acrylic, methacrylic, itaconic, crotonic, vinylsulfonic or 0000 N-methacryioyl-aminopropanesulfcnic acid. 04 20 As inorganic neutralizing agent, there may be used 4 0*
ammonium hydroxide or an alkali metal hydroxide such as 0000 a 00 0 0 lithium hydroxide, sodium hydroxide or potassium hydroxide, or an alkaline earth metal hydroxide such as magnesium hy- droxide or caicium hydroxide, and furthermore zinc oxide. 0000 O 00 00 0 25 Instead of one of these agents, a mixture of several of *0000 a them may be employed alternatively. The amount has to be chosen in such a manner that the intended neutralization degree is attained; it is in the range of from 0.02 to 1.2, preferably 0.12 to 1, base equivalent (relative to 1 mol of maleic anhydride in the copolymer). Depending on the kind and amount of neutralizing agent, a copolymer solution or dispersion is obtained; for the preparation of a solution, a larger amount of neutralizing agent is used than for the preparation of a dispersion. For preparing an acidic solution of a hydrolyzed sty- rene/maleic anhydride copolymer it is recommended to carry out the alkaline treatment in the presence of an emulsi-
5 HOE 79/F 253
fier, preferably an anionic emulsifier. Suitable emulsi- fiers are especially alkali metal salts or ammonium salts of alkylsulfonic, arylsulfonic or alkylarylsulfonic acids or the corresponding sulfuric, phosphoric or phosphonic acids, the cited compounds possibly containing ethylene oxide units between the hydrocarbon radical in question (having preferably from 10 to 18 carbon qtoms) and the an- ionic group; the oxethylated compounds contain preferably from 5 to 30 ethylene oxide units Examples of suitable emulsifiers are sodium laurylsulfate, sodium octylphenol- glycol ether sulfate, sodium dodecylbenzene sulfonate, sodium lauryldiglycol sulfate, and the ammonium salts of oxethylated and sulfated tri-t.-butylphenol, t.-butylphenol and nonylphenol. 15 The emulsifier is used in an amount of from 3 to 100, preferably 5 to 25, by weight (relative to the styrene/ maleic anhydride copolymer). The copolymer dispersion may be converted to a solu- 0o.. tion by heating it to a temperature within the abovemen- 020 tioned range of treatment temperature after having added an emulsifier of the cited kind. The aqueous solution or dispersion of a hydrolyzed co- polymer of styrene and maleic anhydride according to the invention has an acidic reaction. Its pH is below 7, pre- 25 ferably below 6; especially advantageous is a solution or dispersion having a pH of from 2.0 to 5.7. The copolymer content of the solution or dispersion is in the range of from 5 to 50, preferably 10 to 30, by weight, and its viscosity is from 20 to 20,000, preferably 50 to 3,000 mPa.s (measured according to Epprecht). The copolymer solution or dispersion of the invention is applied as emulsifying, dispersing sizing, gluing, thickening, flocculating or hydrophobizing agent, and as coating or binder in the fields of textile, paint and varnish, adhesives and paper manufacture. The dissolved or dispersed copolymer is fixed to materials such as wood, paper, ceramics, metals or plastics by applying the
6 HOE 79/F 253
solution or dispersion thereto and removing the water, or by electrochemical deposition. The solution or dispersion is excellently suitable for stabilizing aqueous dispersions of natural or synthe- tic, inorganic or organic substances. for example cellu- lose, plastics, pigments or fillers. It is furthermore applied for the suspension or emulsion polymerization of vinyl compounds, especially vinyl esters and acrylic esters. The plastics dispersions so stabilized have an increased stability to shearing forces and pigments. The noment of adding the stabilizer solution or dispersion is irrelevant; it may be added with similar results during or after the c* preparation of the dispersion to be stabilized. The copolymer solution or dispersion of the invention is applied above all in the polymerization of vinyl com- pounds in an aqueous medium under acidic conditions. Espe- cially suitable monomers are olefinically unsaturated com- pounds of the formula
H2 C C R1 "'2 2 R o
in which R1 is a hydrogen atom or a methyl radical, and R2 is a) an alkylcarboxyl radical having from 2 to 18, preferably 2 to 12, carbon atoms, b) an alkoxy radical having from 1 to 4 carbon atoms, c) a nitrile group, d) a halogen atom, preferably chlorine, e) a carboxyl or sulfo group, f) an alkoxycarbonyl radical having from 2 to 12, prefer- ably 2 to 9, carbon atoms, g) an aminocarbonyl radical, h) a hydrogen atom, i) a phenyl radical, or k) a vinyl radical.
7 HOE 79/F 253
Examples of such olefinically unsaturated compounds are a) vinyl esters of aliphatic carboxylic acids having from 2 to 18, preferably 2 to 12, carbon atoms, such as vinyl acetate., vinyl propionate, vinyl butyrate, vinyl piva- late, vinyl isononate, vinyl laurate or vinyl decanates, furthermore vinyl esters of a mixture of monocarboxylic acids having from 9 to 11 carbon atoms; b) vinyl ethers, such as vinylmethyl ether, vinylethyl ether or vinyl-n-butyl ether; c) acrylonitrile or methacrylonitrile; d) vinyl halides, such as vinyl chloride or allyl chloride; e) unsaturated monocarboxylic acids such as acrylic, meth- acrylic or vinylsulfonic acid; f) acrylic esters or methacrylic esters of monohydric alka- nols having from 1 to 11, prefrably 1 to 8, carbon atoms, such as methyl acrylate, ethyl.acrylate, butyl acrylate, 2-etLylhexyl acrylate, methylmethacrylate, ethylmeth- acrylate, butylmethacrylate, hexylmethacrylate, octyl- methacrylate or 2-ethylhexylmethacrylate; g) acrylic or methacrylic acid amides such as acrylic, N- methylolacrylic, methacrylic or N-methylolmethacrylic acid amide; h) ethylene; i) styrene or methylstyrene; or k) butadiene or isoprene. Especially suitable monomers are the vinyl esters a), the vinyl ethers the vinyl halides d) and the acrylic and methacrylic esters The monomers are used per se or as mixtures with one another; monomer combinations are for example obtained from an acrylic ester and a methacry- lic ester', an acrylic or methacrylic ester and a vinyl ester, a mixture of different vinyl esters, especially vinyl acetate and vinyl esters of a mixture of monocarboxy- lie acids having from 9 to 11 carbon atoms, furthermore from vinyl acetate and ethylene, or from vinyl acetate, ethylene and vinyl chloride. The polymerization is usually carried out in the pre-
8 HOE 79/F 253
sence of a free radical-forming initiator, preferably a peroxide compound or an aliphatic azo compound. The ini- tiator is oil-soluble or, preferably, water-soluble, and used in an amount of from 0.05 to 2, preferably 0.1 to 1, by weight (relative to the total amount of monomers). Suitable are especially hydrogen peroxide, alkali metal or ammonium salts of persulfuric, peroxydisulfuric or peroxy- diphosphoric acid, for example sodium persulfate, potassium peroxydisulfate or ammonium peroxydisulfate; furthermore alkylhydroperoxides such as t.-butyl hydroperoxide; dialkyl peroxides such as di-t.-butyl peroxide; diacyl peroxides such as diacetyl peroxide, dilauroyl peroxide or dibenzoyl peroxide; furthermore azo-di-isobutyric acid nitrile, azo- L dicarbonamide or azo-,/ bis(4-cyanovaleric acid). The o 15 initiator is optionally used in combination with a reducing agent, especially an ammonium salt, alkali metal salt or alkaline earth metal salt of a sulfur-containing acid hav- ing a reducing action; suitable are preferably sulfites, bisulfites, pyrosulfites, dithionites, thiosulfates or S 20 formaldehyde sulfoxylates. Tne amount of reducing agent is from 0.05 to 20, preferably 0.5 to 10, by weight (relative to the styrene/maleic anhydride copolymer). For inureasing the polymerization speed, it is advan- tageous to use a solution or dispersion of a hydrolyzed 25 styrene/maleic anhydride copolymer which has been prepared in the presence of a sulfite. Suitable sulfites are neu- tral or acidic salts of sulfurous or pyrosulfurous acid, especially ammonium, alkali metal or alkaline earth metal salts, and the amounts to be used are from 0.05 to 20, pre- ferably 0.5 to 10, by weight (relative to the styrene/ma- leic anhydride copolymers). In emulsion polymerization, the solucion or dispersion of the hydrolyzed styrene/maleic anhydride copolymer is used in such an amount that the copolymer is present in a quantity of from 0.1 to 10, preferably 0.5 to 5, by weight (relative to the total amount of monomers). In suspension polymerization, from 0.01 6o 2 and preferably 0.05 to 1,
HOE 79/F 253
by weight (relative to the total amount of monomers) are sufficient. Polymerization is carried out at a tempera- ture of from 25 to 90 0 C, preferably 40 to 750 C. Depending on the kind and amount of the monomers in question the po- lymerization time is in the range of from 2 to 8, prefer- ably 2.5 to 5, hours. The resulting polymer dispersions are excellently stable to shearing forces and have a very good pigment- binding capacity. Therefore, they are applied above all as binder dispersions in paiits, especially dispersion paints, and paper coating compositions. The paper so coated is distirguished by high wet pick resistance and water re- sistence of crating (determined be measuring the wet rub in a so called Taber-Abraser). The following examples illustrate the invention, the percentages being by weight in all cases.
EXAMPLE 1: In a vessel provided with agitator and reflux conden- ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 2:1) having an average molecular weight of 1,700 are heated for 2 hours at a temperature of 95 100 0 C together with 790 g of water and 7.05 g of caustic soda, and then cooled to room temperature. A clear solu- tion having a pH of 4.7 and a polymer content of 16.5 is obtained. The carboxyl groups of the hydrolyzed copolymer are neutralized to an extent of 18
EXAMPLE 2: a) Example 1 is repeated; however, instead of 7.05 g of caustic soda, 3.52 g only are used and the water amount is 720 g instead of 790 g. Moreover, the reac- tion mixture is filtered after cooling to room tempera- ture, thus obtaining a residue of 30.9 g (after drying). As filtrate,, a dispersion having a pH of 4.1 and a poly- mer content of 14.9 is obtained. b) 8 g of the dispersion obtained according to a) are n~
10 HCE 79/F 253
heated to 70 0 C together with 2 g of a 15 aqueous solu- tion of sodium laurylsulfate, thus causing the copolymer to be dissolved. c) 8 g of the dispersion obtained according to a) are heated to 80 0 C together with 2 g of a 15 aqueous solu- tion of the ammonium salt of a nonylphenol oxethylated with 25 mol of ethylene oxide and then sulfated as emul- sifier, thus dissolvirg the copolymer.
EXAMPLE 3: In a vessel provided with agitator and reflux conden- ser, 300 g of a copolymer of styrene and maleic arhydride (molar ratio 3:1) having an average molecular weight of 1,900 are heated for 2 hours at a temperature of 96 0 C to- gether with 1,680 g of water and 29.3 g of caustic soda, and then cooled to room temperature. A solution having a pH of 6.8 and a polymer content of 16.7 is obtained. 50 of the carboxyl groups of the hydrolyzed copolymer are neu- tralized.
EX A P L E 4: In a vessel provided with agitator anc reflux conden- ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) having an average molecular weig.t of 1,900 are heated for 2 hours at a temperature cf 100 0 C to- gether with 79u g of water and 25 g of a 25 aqueous ammo- nia solution, and then cooled to room temperature. A solu- tion having a pH of 6.8 and a polymer content of 16.1 is obtained. 50 of the carboxyl groups of tne hydrolyzed copolymer are neutralized.
EXAMPLE a) In a vessel provided with agitator and reflux con- denser, 150 g of a copolymer of styrene and maleic an- hydride (molar ratio 3:1) having an average molecular weight of 1,900 are heated for 3 hours at a temperature of 97°C together wi.i 720 g of water and 7.3 g of caustic
11 HOE 79/F 253
soda, and then cooled to room temperature. A dispersion having a ph of 5.6 and a polymer content of 17.6 is obtained. 25 of the carboxyl groups of the hydrolyzed copolym~ers are neutralized. 'he mean diameter of the dispersed polymer particles is 0.038 um. b) 8 g of the dispersion obtained a 2ccrdirg to a) are heated to 85 00 togo-her with 2 g of a 15 aqueous solu- tion of sodium laurylsulfate, thus dissolving the copo- 1lymer.
C) 8 g of tho. dispersion obtained according to a) are heated tc 900% together with 2 g of the 15 aqueous so- lution of the vw ~lsifier of Example 2c), thus dissolving the copolymer.
E X A M P L :s 6 to 8: In a vessel provided with agitator and reflux conden- ser, 150 g each of a copolymer of styrene and malei, anThy- dride (m.olar ratio 3:1) having an average molecular weight of 1,900 are heated for varying periods of time to a temn- perature of 97 0 C together with 720 g each of water and different amounts of lithium hydroxide, and then cooled to room temperature. Details and properties of the solution or dispersion in question are listed in Table 1.
Table 1
Example 6 7 8 amount LiOl 4. 3.3 2.2 time of treatment 2 2 3 result solution dispersion dispersion pH4 5.3 5.1 4I.7 polymer content 17.6 17.3 16.9 neutralized 25 18.7 12.5 carboxyl groups
12 HOE '91F 253
EXAMPLE 9: In a vessel provided with agitator and reflux con .en- ser, 150 g of a copolymer of styrene and maleic anhydric (molar ratio 3:1) having an average molecular weight of 1,900 are heated under a nitrogen blanket for 2 hours at a temperature of 96 0 C together with 1,300 g of water/ 7.3 g of caustic soda, 125 g of a 30 solution of the emulsifier of Example 2c) and 12 g of sodium pyrosulfite, and then cooled to room temperature. A solution having a pH of 5.3 and a polymer content of 13.3 is obtained. 25 of the carboxyl groups of the hydrolyzed copolymer are ne'itralized. The solution is adjusted with water to a concentration of 7.8 for application in the polymerization of vinyl acetate. o E X A M P L E In a vessel provided with agitator and reflux conden- ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 2:1) having an average molecular weight of 1,700 are heated for 2 hours under a nitroger blanket to a temperature of 960 C together with 1,300 g of water, 7.3 g of caustic soda, 125 g of a 30 aqueous solution of the emulsifier of Example 2c) and 12 g of sodium pyrosulfite, and then cooled to room temperature. A solution having a 25 pH of 4.3 and a polyme2 content of 13 is obtained. 18.6 of the carboxyl groups of the hydrolyzed copolymer are neu- tralized. The solution is adjusted with water to a concentration of 7.8 for use in the polymerization of 'iinyl acetate.
EXAMPLE OF APPLICATION 1: 510 g of water, 1.77 g of a 6 aqueous sodium alkyl-- sulfonate solution (mean chain length of the alkyl group: 12 to 14 carbon atoms), and 2 g of a 30 aqueous solution of the ammonium salt of nonylphenol oxethylated with 25 mols of ethylene oxide and then sulfated are introduced into a vessel provided with agitator, and then flushed with nitro-
13 HOE 79/F 253
gen. After having added a solution of 2.25 g of an~rmnium persulfate in 20 g of water, the mixture is heated to a temperature of 50 C. While maintaining this temperature, 750 g of vinyl acetate and a solution of 0.39 g of sodium formaldchyde-sulfoxylate in 50 g of water Pie added sepa- rately and uniformly within 3 hours to tne mixture. With- in the 1st hour, the same amount of the emulsifier combi- nation is added again to the batch; within the following 2 hours, 100 g of tne copolymer solution obtained according 13 to Example 9 anu 1.87 g of the above alKvlsulfonate solu- tion and 21.2 g of the above 30 ammonium salt solution ai-e added in corresponding doses, Subsequently, a solution of 0.75 g of ammonium persulfate in 30 g of water is added to the mixture, and the batch is heated for 30 minutes to 75 C and then cooled to room temperature. A coagulate-free polyvinyl acetate dispersion is ob- tained which is adjusted to pH 6 with 3.2 g of 12.5 ammonia solution. The solids content of the dispersion is 50.8 and the polymer particles have a mean diameter of 0.22 /um. The dispersion is stable to shearing.after a 2 minutes' agitation by means of a high-speed agitator (5000 rpm) no coagulate fcrmation can be observed, and the mean particle size of the polymer has not changed.
EXAMPLE OF APPLICATION 2: Example of application 1 is repeated; however, the co- polymer solution of Example 10 is used instead of thai of Example 9. The polyvinyl acetate dispersion obtained is coagulate-free. The solids content of the dispersion is 50.4 and the polymer particles have a mean diameter of 0.18 /um. The dispersion is stable to shearing (test ac- cording to Example of application 1).
COMPARATIVE EXAMPLE 1: 1,620 g of the styrene/maleic anhydride copolymer used in Example 3 are agitated for 6 hours 3/4 at a temperature of 80°C in 8,024 g of water with addition of 316 g of
116±56/2I
14 HOE 79/F 253
caustic soda. The suspension obtained after cooling to room temperature is filtered, thus obtaining a solid resi- due of 47 g. The filtrate has a pH of 10.0 and a polymer content of 18.7 100 of the carboxyl groups of the hydrolyzed copolymer are neutralized.
COMPARATIVE EXAMPLE 2: Example 4 is repeated; however, the temperature of 0 heating is 70 C only. 50 only of the styrene/maleic anhydride copolymer are dissolved; the solution has a pH of 5.2.
COMPARATIVE EXAMPLE 3: Example 4 is repeated, the temperature of heating be- 15 ing only 70 0 C, and the double amount of ammonia solution is used. The solution obtained has a pH of 9.3.
COMPARATIVE EXAMPLE 4: Example of application 1 is repeated while replacing 20 the copolymer solution obtained in Example 9 by water. The polyvinyl acetate dispersion obtained coagulates in S the test for stability to shearing.
COMPARATIVE EXAMPLE Example of application 1 is repeated while replacing the copolymer solution obtained in Example 9 by a corres- pondingly prepared solution of a styrene/maleic anhydride copolymer (molar ratio 1:1) having an average molecular weight of 1,600, the carboxyl groups of which being neu- tralized to an extent of 12.3 after hydrolysis. The polyvinyl acetate dispersion obtained coagulates in the test for stability to shearing.
1. Aqueous s, mer of st, ratio of: of from 1 to 80,000. the copol, ion or di,,
02. The soluti polymer he 0~ of from 1.
The soluti
0 polymer ha (numerical
4. The soluti 6 to 50 pe 0000 are neutra
A process or dispers maleic anh anhydri de an mnorgan ing a copo maleic anh weight of to 2500 of such an or alkalin
IW.4
Claims (4)
1. Aqueous solution or dispersion of a hydrolyzed copoly- 1 mer of styrene and maleic anhydride wherein the molar K ratio of styrene to maleic anhydride is in the range i of from 1.5:1 to 6:1, the molecular weight is from 500 to 80,000, 1 to 60 percent of the carboxyl groups of i the copolymer are neutralized, and the pH of the solut- ion or dispersion is below 7.
k 2. The solution or dispersion of claim 1, wherein the co- polymer has a molar ratio of styrene to maleic anhydride oo of from 1.6:1 to 4:1. o oP
3. The solution or dispersion of claim 1, wherein the co- o o polymer has a molecular weight of from 800 to 30,000 (numerical average).
4. The solution or dispersion of claim 1, wherein from f o* 6 to 50 percent of the carboxyl groups of the copolymer are neutralized.
5. A process for the preparation of an aqueous solution or dispersion of iydrolyzed copolymer of styrene and maleic anhydride by hydrolysis of a styrene/maleic anhydride copolymer and partial neutralization with an inorganic neutralizing agent, which comprises heat- ing a copolymer having a molar ratio of styrene to I maleic anhydride of from 1.5:1 to 6:1 and a molecular weight of from 500 to 80,000 to a temperature of from to 250 0 C in the presence of water and in the presence I of such an amount of ammonia, an alkali metal hydroxide or alkaline earth metal hydroxide, or zinc
I
16 HOE 79/F 253
oxide that is sufficient to neutralize 1 to 60 percent of the carboxyl groups of the copolymer.
6. The process of claim 5, which comprises using the cope- lymer in a concentration of from 5 to 50 by weight (relative to the total amount of copolymer and water).
7. The process of claim 5, which comprises hea±ting in the presence of an anionic emulsifier.
DATED this 18th day of September 1980. S. e HOECHST AKTIENGES ELLSCHAFT A
4 4
C.4' 4 44 4, 4
C S. EDWD. WATERS S01VS PATENT ATTORNEYS QUEEN STREET MELBOURNE. VIC. 3000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29384290 | 1979-09-22 | ||
| DE19792938429 DE2938429A1 (en) | 1979-09-22 | 1979-09-22 | AQUEOUS SOLUTION OR DISPERSION OF A STYRENE / MALEIC ACID ANHYDRIDE COPOLYMER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6255180A AU6255180A (en) | 1981-04-09 |
| AU537112B2 true AU537112B2 (en) | 1984-06-07 |
Family
ID=6081599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU62551/80A Ceased AU537112B2 (en) | 1979-09-22 | 1980-09-19 | Hydrolysed styrene-maleic anhydride copolymers |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0025979B1 (en) |
| JP (1) | JPS5647412A (en) |
| AR (1) | AR222101A1 (en) |
| AT (1) | ATE3555T1 (en) |
| AU (1) | AU537112B2 (en) |
| BR (1) | BR8005999A (en) |
| CA (1) | CA1161581A (en) |
| DE (2) | DE2938429A1 (en) |
| DK (1) | DK156579C (en) |
| ES (1) | ES8105356A1 (en) |
| FI (1) | FI72990C (en) |
| IE (1) | IE50353B1 (en) |
| MX (1) | MX156364A (en) |
| NO (1) | NO802786L (en) |
| PT (1) | PT71820B (en) |
| ZA (1) | ZA805810B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU620235B2 (en) * | 1989-10-25 | 1992-02-13 | Ausidet S.R.L. | Process for the manufacture of aqueous solutions of anti-scaling agents and thus obtained solutions |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5017985A (en) * | 1984-11-05 | 1986-06-03 | Owens-Corning Fiberglas Corporation | Glass fiber size and impregnant compositions |
| DE3631814A1 (en) * | 1986-09-19 | 1988-03-31 | Basf Ag | LIGHTLY CROSSLINKED, WATER-SOLUBLE POLYMAL ACID, METHOD FOR THE PRODUCTION AND USE THEREOF |
| ATE165252T1 (en) * | 1989-06-06 | 1998-05-15 | Pluss Stauffer Ag | HIGHLY CONCENTRATED AQUEOUS SUSPENSION OF MINERALS AND/OR FILLERS AND/OR PIGMENTS |
| JPH07157524A (en) * | 1993-11-24 | 1995-06-20 | Union Carbide Chem & Plast Technol Corp | Vinyl copolymer containing macromonomer |
| FI991295A7 (en) * | 1999-06-07 | 2000-12-08 | Neste Chemicals Oy | Process for preparing styrene-maleic hydride copolymers |
| EP1405865A1 (en) * | 2002-10-04 | 2004-04-07 | DSM IP Assets B.V. | Process for preparing a polymer dispersion |
| JP5207097B2 (en) * | 2006-06-16 | 2013-06-12 | 星光Ｐｍｃ株式会社 | Filler modifier, filler slurry and paper making method |
| JP5515217B2 (en) * | 2008-01-11 | 2014-06-11 | 東洋インキＳｃホールディングス株式会社 | Dispersant, and pigment composition and pigment dispersion using the same |
| JP5614786B2 (en) * | 2013-05-09 | 2014-10-29 | 株式会社Adeka | Novel polymer and non-aqueous electrolyte secondary battery using the polymer |
| WO2015099170A1 (en) * | 2013-12-27 | 2015-07-02 | コニカミノルタ株式会社 | Acrylic resin film and method for manufacturing same, polarizing plate protective film, and polarizing plate and liquid crystal display device including polarizing plate protective film |
| JP7115427B2 (en) * | 2018-07-11 | 2022-08-09 | 荒川化学工業株式会社 | Tackifying resin emulsion, water-based adhesive/adhesive composition, and adhesive/adhesive sheet |
| KR20240033249A (en) * | 2021-07-15 | 2024-03-12 | 산 노프코 가부시키가이샤 | Dispersants and water-based coating compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490489A (en) * | 1944-02-03 | 1949-12-06 | Du Pont | Process for copolymerizing maleic anhydride and styrene |
| US3444151A (en) * | 1965-09-07 | 1969-05-13 | Sinclair Research Inc | Styrene-maleic anhydride-amine polymers as emulsifiers in polymerization of vinyl monomers |
| GB1414918A (en) * | 1973-02-14 | 1975-11-19 | Ciba Geigy Uk Ltd | Treatment of water to prevent the deposition of scale |
| US3835122A (en) * | 1973-04-25 | 1974-09-10 | Atomic Energy Commission | Novel polystyrene product having rapid-post-irradiation decay of conductivity and process of making same |
| US3939108A (en) * | 1974-12-16 | 1976-02-17 | National Starch And Chemical Corporation | Cold water resistant starch-based adhesive containing styrene-maleic anhydride resin and fixed alkali |
| JPS5299104A (en) * | 1976-02-17 | 1977-08-19 | Toyo Ink Mfg Co | Composition of water dispersive material |
| JPS54107945A (en) * | 1978-02-14 | 1979-08-24 | Toagosei Chem Ind Co Ltd | Aqueous dispersion of finely granulated polymer |
-
1979
- 1979-09-22 DE DE19792938429 patent/DE2938429A1/en not_active Withdrawn
-
1980
- 1980-09-16 ES ES495100A patent/ES8105356A1/en not_active Expired
- 1980-09-18 DE DE8080105591T patent/DE3063516D1/en not_active Expired
- 1980-09-18 AT AT80105591T patent/ATE3555T1/en not_active Application Discontinuation
- 1980-09-18 EP EP80105591A patent/EP0025979B1/en not_active Expired
- 1980-09-18 FI FI802934A patent/FI72990C/en not_active IP Right Cessation
- 1980-09-19 PT PT71820A patent/PT71820B/en unknown
- 1980-09-19 ZA ZA00805810A patent/ZA805810B/en unknown
- 1980-09-19 BR BR8005999A patent/BR8005999A/en unknown
- 1980-09-19 CA CA000360619A patent/CA1161581A/en not_active Expired
- 1980-09-19 JP JP12939380A patent/JPS5647412A/en active Granted
- 1980-09-19 IE IE1958/80A patent/IE50353B1/en not_active IP Right Cessation
- 1980-09-19 AU AU62551/80A patent/AU537112B2/en not_active Ceased
- 1980-09-19 DK DK399380A patent/DK156579C/en active
- 1980-09-19 NO NO802786A patent/NO802786L/en unknown
- 1980-09-19 AR AR282593A patent/AR222101A1/en active
- 1980-09-22 MX MX184014A patent/MX156364A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU620235B2 (en) * | 1989-10-25 | 1992-02-13 | Ausidet S.R.L. | Process for the manufacture of aqueous solutions of anti-scaling agents and thus obtained solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1161581A (en) | 1984-01-31 |
| PT71820A (en) | 1980-10-01 |
| DK156579B (en) | 1989-09-11 |
| IE50353B1 (en) | 1986-04-02 |
| ES495100A0 (en) | 1981-06-16 |
| IE801958L (en) | 1981-03-22 |
| ES8105356A1 (en) | 1981-06-16 |
| JPS5647412A (en) | 1981-04-30 |
| JPH0336854B2 (en) | 1991-06-03 |
| ATE3555T1 (en) | 1983-06-15 |
| FI72990C (en) | 1987-08-10 |
| PT71820B (en) | 1981-10-23 |
| DK399380A (en) | 1981-03-23 |
| AR222101A1 (en) | 1981-04-15 |
| DE2938429A1 (en) | 1981-04-09 |
| FI72990B (en) | 1987-04-30 |
| NO802786L (en) | 1981-03-23 |
| EP0025979B1 (en) | 1983-05-25 |
| MX156364A (en) | 1988-08-15 |
| ZA805810B (en) | 1981-10-28 |
| DK156579C (en) | 1990-01-29 |
| DE3063516D1 (en) | 1983-07-07 |
| EP0025979A1 (en) | 1981-04-01 |
| FI802934A7 (en) | 1981-03-23 |
| AU6255180A (en) | 1981-04-09 |
| BR8005999A (en) | 1981-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU536655B2 (en) | m | |
| AU528687B2 (en) | Intumescable fire-retardent granules | |
| AU535049B2 (en) | Secretafacient device | |
| AU529403B2 (en) | Polyetheramide/imide | |
| AU5655280A (en) | Breathalyser device | |
| AU5511080A (en) | Tap | |
| AU536766B2 (en) | Transducer position control | |
| AU6255180A (en) | Hydrolysed styrene-maleic anhydride copolymers | |
| AU5490680A (en) | Limit switch | |
| AU522431B2 (en) | Thermal switch unit | |
| AU5642480A (en) | Boiler | |
| AU532613B2 (en) | Olefin copolymers | |
| AU522877B2 (en) | Olefin/maleic acid anhydride copolymers | |
| AU526389B2 (en) | Dartboard | |
| AU529992B2 (en) | Tert-butyl-styrene copolymers | |
| AU5526280A (en) | Hand control | |
| AU4008778A (en) | Maleic anhydride copolymers | |
| AU5966380A (en) | Movable targets | |
| AU514047B2 (en) | Maleic anhydride copolymers | |
| AU513110B2 (en) | Ladle | |
| AU531153B2 (en) | Coaling of anhydride copolymers | |
| AU531503B2 (en) | Block copolymers | |
| AU530665B2 (en) | Microorganism-culturing device | |
| AU6048680A (en) | Boiler | |
| AU506705B3 (en) | Fumigation lance |