DE1213995B - Process for the production of polyesters by polymerizing lactones - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C08g

German class: 39 c -16

Number: 1213 995

File number: U4474IVd / 39c

Filing date: April 9, 1957

Opening day: April 7, 1966

The invention is a method for Production of polyesters by polymerizing lactones in the presence of to open the lactone ring capable organic compounds and acidic inorganic compounds as catalysts, which is characterized in that one lactones of the general formula

RCH- (CRa) _n -C =

ο

in which η is at least 4, R is a hydrogen atom or an alkyl, cycloalkyl, alkoxy or aryl radical, the total number of carbon atoms of the substituents R on the lactone ring not exceeding 12 and at least η + 2 of the radicals R being hydrogen atoms, in the presence polymerized organic compounds having at least one hydroxyl or amino group and of sulfuric acid, phosphoric acid, hydrochloric acid, boron trifluoride or zinc chloride at temperatures of 20 to 18O ⁰ C. It is known that y-butyrolactone or σ-valerolactone react with a polyhydric alcohol in the presence of sulfuric acid at temperatures between 190 and 25O ⁰ C to polyesters having terminal carboxyl groups. It is also known that σ-valerolactone, thus polymerizing the lactone with five carbon atoms in the lactone ring, with or without addition of a catalyst in a sufficiently long time of about 10 hours at temperatures above 15O ⁰ C, but that lactones having six carbon atoms in the lactone ring substantially heavier are to be polymerized and that the difficulties in the polymerization increase as the number of carbon atoms in the lactone ring increases. The invention has shown that the polymerization of the lactones used according to the invention with six or more carbon atoms in the lactone ring can surprisingly be carried out in significantly more favorable times and even at temperatures of 20 to 180 ^° C., and that no discoloration occurs and very stable polyesters are obtained . It is precisely the known sensitivity of the polyesters per se with respect to discoloration phenomena when using catalysts would have led one to expect that discoloration cannot be avoided in the case of the higher lactones. Polymers made from lactones with five or fewer carbon atoms have a tendency to convert back to the monomer, especially at higher temperatures. Polyesters made from lactones with six or more carbon atoms in the lactone ring do not have this disadvantage either.

Process for the production of polyesters by
Polymerization of Lactones

Applicant:

Union Carbide Corporation,
New York, NY (V. St. A.)

Representative:

Dipl.-Chem. Dr. H.-G. Eggert, patent attorney,
Köm-Lindenthal, Peter-Kintgen-Str. 2

Named as inventor:
Fritz Hostettler, Charleston, W.Va .;
Leland Clarence Shriver,
South Charleston, W.Va. (V. St. A.)

_ao claimed priority:

V. St. v. America dated April 13, 1956 (577 953)

as The method of the invention is conducted at temperatures from 20 to 180 ⁰ C, in particular between 60 and 120 ⁰ C is performed. The catalyst concentration can be between 0.001 percent by weight, based on the weight of the lactone, up to 0.5 percent by weight, preferably between 0.01 and 0.1. Percent by weight, fluctuate. If hydrochloric acid is used as a catalyst, the concentration can even be 2.5 percent by weight.

Particularly suitable substituted ε-caprolactones are for example the various monoalkyl caprolactones, z. B. the monomethyl, monoethyl, Monopropyl, monoisopropyl to monododecyl caprolactone; Dialkyl-e-caprolactone, in which the both alkyl groups on the same or different carbon atoms, but not both on the ε-carbon atom are substituted; Trialkyl-e-caprolactone, in which three carbon atoms are substituted on the lactone ring, provided that the ε-carbon atom is not disubstituted; Alkoxy-e-capro-

lactones, such as methoxy- and ethoxy-s-caprolactone, and cycloalkyl and aryl-e-caprolactones, such as cyclohexyl and phenyl-e-caprolactone and lactones with more than 6 carbon atoms, in the ring, ζ. Β. f-oenantholactone.

According to the invention, organic compounds serve as initiators for opening the lactone ring with at least one hydroxyl or amino group.

609 557/342

3 4

These initiators include monohydric alcohols, other suitable bifunctional initiators sitfd

and amines, one for opening the; Lactone rings polyethers of monoepoxides with terminal ends

have suitable reactive site, as well as poly-hydroxyl groups formed by polymerizing

functional initiators such as polyols, polyamines and monoepoxides with catalysts and hands

Amino alcohols. 5 of the obtained polymers with alkaline agents

Suitable monohydric alcohols are z, B, alipha- have been prepared in a known manner,

Table alcohols, such as methanol, ethanol, propanol, are also higher-functional alcoholic compounds

Isopropanol, 1-butanol, 2-butanol, tert-butanol, fertilize, including triols, such as glycerine, tri

1-pentanol, 3-pentanol, tert-amyl alcohol, 1-hexanol, methylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol,

4-methyl-3-pentanol, 2-ethyl-1-butanol, 1-heptanol, io N-triethanolamine and N-triisopropanolamine,

3-heptanol, 1-octanol, 2-ethyl-1-hexanol, 1-nonanol, various tetrols such as erythritol, pentaerythritol,

2,6-dimethyl-4-heptanol, 2,6,8-trimethyl-4-nonanol, Ν, Ν, Ν ', Ν'-tetrakis - (2 - hydroxyethyl) - ethylenediamine

5 - ethyl - 2 - nonanol, 7 - ethyl - 2 - methyl - 4 - undecanol, and N, N, N ', N'-tetrakis- (2-hydroxypropyl) -ethylene-

3,9-triethyl-6-decanol and lauryl alcohol, aromatic diamine, pentols, hexols, such as dipentaerythritol and

table alcohols such as benzyl alcohol and phenyl 15 sorbitol, alkyl glycosides, and carbohydrates such as GIu-

methyl carbinol, as well as cycloaliphatic alcohols such as cose, sucrose, starch and cellulose, are suitable.

Cyclohexanol and trimethylcyclohexanol. Other suitable polyols are the polyoxyalkylated

Monovalent aliphatic amines, derivatives of polyfunctional compounds with, are also suitable

such as methyl, ethyl, n-propyl, isopropyl, η-butyl, three or more reactive hydrogen atoms,

sec-butyl, isobutyl, tert-butyl, n-amyl, n-hexyl, e.g. B. the reaction product of trimethylolpropane

and 2-ethylhexylamine; aromatic amines such as _s with 3 to 45 moles of ethylene oxide. Besides the .polyoxy?

Aniline, orthotoluidine and metatoluidine, and cycloalkylated derivatives of trimethylolpropane are suitable

aliphatic amines such as cyclohexylamine. also the polyoxyalkylated derivatives of. föl · ·

The compounds suitable as bifunctional initiators: glycerine, 1,2,4-butanetriol,

Diols include glycols of the general 25 1,2,6-Hexanetriol, Erythritol, Pentaefythfit, Sorbitol, Me-

Formula of glycosides, glucose, sucrose, diamines

HO (CH ₂ ) ^ OH general formula

in which η is 2 to 10, glycols of the general H ₂ N (CH ₂ ) ^ NH ₂

Formern 30 in which η is 2 to 10, 2- (methylamino) ethylamine,

HO (CH ₂ CH ₂ O) »H various phenylene and toluene diamines, benzidine,

j 3,3'-dimethyl-4,4'-biphenyldiamine, 4,4'-methylenedi-

^u aniline, 4,4 ', 4 "-methylidene trianiline, cycloaliphatic

HO [CH (CH ₃ ) CH ₂ O] _m H diamines, such as 2,4-cyclohexanediamine and 1-methyl

35 2,4-cyclohexanediamine, amino alcohols of the general type in which η is 1 to 40, 2,2-dimethyl-1,3-pro formula

pandiol, 2.2 "diethyl-1,3-propanediol, 3-methyl-1,5-pen-HO (CH ₂ ) KNH ₂

tandiol, N-methyl- and N-ethyl-diethanolamine,

Cyclohexanediols, 4,4'-methylene-bis-cyclohexanol, in which η is 2 to 10, diethylenetriamine, tri-4,4'-isopropylidene-bis-cyclohexanol, various 40 ethylene tetramine, tetraethylene pentamine and mellitic xylene diols, hydroxymethyl phenethyl -alcohols, hy- dic acid.

droxymethyl-phenyl-propanols, phenylenediethanols, bifunctional for triggering the lactone polymer

Phenylenedipropanols and heterocyclic diols, such as cationic suitable amino alcohols, are aliphatic 1,4-piperazine diethanol. Amino alcohols of the general formula

Other suitable diols are e.g. B. polyoxyalkylated 45

Derivatives of bifunctional compounds with two HO (CH ₂ ) JiNH ₃

reactive hydrogen atoms. They are obtained by the known reaction of diols in which η is 2 to 10, such as isopropanolamine, general formula also aromatic amino alcohols, such as p-amino ·

50 phenethyl alcohol and p-amino-a-methylbenzyl alcohol, and cycloaliphatic amino alcohols such as 4-aminocyclohexanol.

in which η is 2 to 10, such as propylene glycol, also with suitable higher-functional amino alcohols

Thiodiethanol and xylene diols, 4,4'-methylenediphenol, a total of at least three hydroxy and primary ones 4,4'-Isopropylidenediphenol and resorcinol, from mer-55 or secondary amino groups are among others captoalcohols, such as mercaptoethanol, dicarbon diethanolamine, diisopropanolamm, 2- (2-aminoethyl acids, such as maleic, amber, glutaric, adipic, amino) ethanol, 2 - amino - 2 - (hydroxymethyl) pimeline, Sebacin-, phthal-, tetrahydrophthal- and 1,3-propanediol and 2-amino-2-methyl-1,3-propanediol. Hexahydrophthalic acid, aliphatic, aromatic Suitable diamines include aliphatic

and cycloaliphatic primary monoamines such as 60 diamines of the general formula
Methylamine, ethylamine, propylamine, butylamine,

Aniline, cyclohexylamine, secondary diamines such as H ₂ N- (CH ₂ ) «- NH ₂

Ν, Ν'-dimethylethylenediamines, and secondary ami-,, ... _. . . _n -τ,,

amino alcohols containing no groups, such as N-Me ^and onosecond diamonds of the general formula ethylethanolamine, with alkylene oxides, such as ethylene, 65 R ^ H (CH ₂ ) WNH ₂

Propylene, 2-butylene, isobutylene oxide, butadiene monoxide, styrene oxide and with mixtures of these in which η is 2 to 10 and R "is an alkyl, aryl, monoepoxide or cycloalkyl radical, aromatic diamines,

5 6

such as m-phenylenediamine, p-phenylenediamine, toluene and the reaction are considered complete when

2,4-diamine, toluene-2,6-diamine, 1,5-diamino-naphtha - the refractive index remains constant. Afterward

lin, 1,8-diamino-naphthalene, diamino-meta-xylene, di- is the polyester in a long-necked flask

amino-para-xylene, benzidine, 3,3'-dimethyl-4,4'-biphe- a temperature of 180 to 200 ° C at 2 mm Hg

nyldiamine, 3,3'-dimethoxy-4,4'-biphenyldiamine, 5 heated. Since there are no volatile constituents

3,3 '- dichloro - 4,4' - biphenyldiamine, soft 4,4'-methylene, is / viewed the yield strength of 100 ° _0,

dianiline, 4,4'-ethylenedianiline, 2,3,5,6-tetramethyl- According to analysis, the polyester has a carboxyl number

para-phenylenediamine, 2,5-fluorenediamine and of 0.78, a hydroxyl number of 57.6, a calculated

2,7-fluorenediamine, cycloaliphatic diamines, such as molecular weight of 1935 and no unsaturated

1,4 - cyclohexanediamine, 4,4 '- methylene - bis - cyclo- io bonds,

hexylamine and 4,4'-isopropylidene-bis-cyclohexylamine, example 2
and heterocyclic amines, such as 1,4-bis- (3-amino-

propyl) piperazine. 484.5 g ε-caprolactone, 15.5 g ethylene glycol and

Suitable higher functional polyamines are: 0.060 g of 98% strength sulfuric acid are used as a catalyst

Diethylenetriamine, triethylenetetramine, tetraethylene 15 according to the method of Example 1, but with one

pentamine, dipropylenetriamine, tripropylenetetramine, temperature of 12O ⁰ C and for a time of

Tetrapropylene pentamine, 1,2,5-benzene triamine, toluene - treated for 18 hours.

2,4,6-triamine and tri-4,4 ', 4 "-aminophenylmethane. According to analysis, the yield is 100%, and

Also suitable are vinyl polymers, which in side the polyester has a carboxyl number of 6.38, a

groups along the polymeric molecule, hydroxyl 20 hydroxyl number of 52, an equivalent weight for the

and contain amino groups. Such vinyl poly unsaturated double bonds of 29,480 and one

mers are determined in a known manner, for example by the calculated molecular weight of 1933.
Copolymerization of ethylene and vinyl acetate,

with subsequent saponification of the acetate groups Example 3

manufactured. 25th

Other suitable vinyl polymers include 969 g of a mixture of the isomers of trimethyl

Polyvinyl alcohol copolymers in the well-known ε-caprolactone, 31 g of ethylene glycol and 0.6984 g

, By copolymerization of vinyl monomers to be 98 ° / _o sulfuric acid as a catalyst according to

mers, such as ethylene, reacted with other hydroxyl or the method of Example 1, wherein

However, vinyl monomers containing amino groups receive the reaction temperature 120.degree. C. and the

th, z. B. ortho-, meta-, or para-amino reaction time is 2 hours. Then will

styrene, 3-butene-l, 2-diol, CH ₂ = CH-CHOH-CH ₂ OH, the reaction mixture to a temperature of

Allyl alcohol, methallyl alcohol, 3-phenyl-3-buten-l-ol heated to 186 ° C at a pressure of 1 mm Hg,

and diethylene glycol monovinyl ether. This produces 34 g of a volatile component

To produce a light-colored polyester, 35 and 131 g of polyester are carried out in a yield of 97.7%, the reaction is preferably obtained in the absence of. According to analysis, the polyester has an oxygen. This is z. B. by working in a carboxyl number of 10.7, a hydroxyl number of 61.4, partial vacuum or passing an inert one equivalent weight for the unsaturated double gas, such as nitrogen, through the reaction mixture bonds of 14.470 and a calculated mole. After completion of the polymerization, you can use 40 kular weight of 1510.
any unreacted monomers present by treating in a vacuum at elevated Example 4
Temperatures, e.g. B. at 120 to 200 ° C / l to 5 mm Hg

removed. Since theoretically 1 mole of the organic 182.2 g of y-methyl-e-caprolactone, 544 g of ethylene

compound with at least one hydroxyl glycol and 0.118 g of 85% phosphoric acid as a catalyst

or amino group (initiator) for the polymerization are lyser according to the method of Example 1

a large number of lactone molecules is sufficient, converted, but at 120 ° C and for a time

the amount of initiator with respect to the lactone of 10.33 hours,

be very low. The yield is 99% and the polyester has

The molecular weight of the invention her- 5 ° according to analysis a carboxyl number of 0.76, a

adjustable polyester can be within a wide hydroxyl number of 46.5, an equivalent weight for

Range and be up to 12,000. the unsaturated double bonds of 158.5 and

The polyesters which can be prepared according to the invention have a calculated molecular weight of 2350.
to react with isocyanates to form high molecular weight polyurethanes and as plasticizers. 55 Example5

The invention is illustrated in the following examples. 114 g of ε-caprolactone, 156 g of a mixture of isomeric Trimethyl-e-caprolactone, 8.36 g ethylene glycol

Example 1 ^an d 0.2088 g of 98 ° / _o by weight sulfuric acid as a catalyst

60 are reacted at 120 ° C for 2.75 hours, wherein

182.2 g of e-caprolactone, 5.44 g of ethylene glycol and the ε-caprolactone first in amounts of about 23 g

0.1269 g of 98 ° / ₀ sulfuric acid as a catalyst advertising and then at half-hour intervals as long

which is added at 25 to 27 ° C for 16 hours in a very pure state, until a total of 114 g have been added

Nitrogen atmosphere kept by a slower. The reaction mixture is then up to

Nitrogen flow during the entire duration of the experiment 65 to a temperature of 186 ° C at 2 mm Hg pressure

is passed through the reaction mixture. The heated, whereby 24 g of a volatile substance,

The course of the reaction is obtained from the regular discussion of a polyester yield of 91.4%.

refractive index tuning can be continuously monitored.

According to analysis, the polyester has a carboxyl number of 1.03, a hydroxyl number of 52.2 and a . calculated molecular weight of 2090.

Example 6

242 g ε-caprolactone, and 0.310 g of boron trifluoride etherate 7,75ig ethylene glycol (47% BF ₃₎ as a catalyst are heated to 12O ⁰ C for 3 hours, then the reaction mixture is heated at 3 mm Hg up to a temperature of 190 ⁰ C.

The polyester yield is 100%, the hydroxyl number is 55.6, the carboxyl number 8.28, and the calculated Molecular weight 1885. There are no unsaturated bonds.

Example 7

About 170 ecm of dry hydrogen chloride (about 0.25 g) measured with a small glass rotameter are added to a mixture of 350 g of ε-caprolactone and 11.2 g of ethylene glycol. The temperature is then increased to about 35 ° C. and the reaction is continued for 5.5 hours, the yield determined on the basis of the refractive index being 42%. An additional estimated amount of 0.25 g of dry hydrogen chloride is then added and the reaction is continued for 2 hours at 35 ° C., a yield of 81% being obtained. A third amount of 0.25 g dry hydrogen chloride is then added and the temperature is ^{increased to 43 °} C. over a further 2 hours. Measurements of the refractive index indicate a yield of practically 100% at this point in the process.

Various titrations between hydrochloric acid additions indicate that 0.71 g had been added while the gauges indicate 0.75 g. The reaction mixture is then ^{freed from by-products at 200 °} C. and a pressure of 1 mm Hg.

The obtained polyester has a hydroxyl value of 54.6, a carboxyl value of 4.0 and a calculated Molecular weight of 1915.

Example 8

1938 g of e-methyl-e-caprolactone are 62 g Ethylene glycol reacted to make a polyester with a molecular weight of 2000 in one yield of 100%. The table below provides information on the catalyst, catalyst concentration, Polymerization times and temperature as well as yield and degree of dehydration, expressed as equivalent weight per double bond, given:

catalyst Kataly
sator in
Weight
percent time in
hours Tempe
rature
⁰ C the end
prey
% Equi
valent
weight
Per
Double
binding H ₂ SO ₄ ....
H ₂ SO ₄ ....
BF ₃
HCl 0.052
0.053
0.075
1.18 25.00
1.75
4.66
10.50 90
120
120
120 100.0
98.0
95.6
100.0 2326
1218
1083
7970

It can be seen from the results that with highly active catalysts such as sulfuric acid and boron trifluoride, the yield is improved and the tendency towards dehydration is reduced by operating at lower temperatures, and that with a relatively weak catalyst such as hydrogen chloride, 100% ige yield and a much smaller amount of unsaturated bonds is obtained, ίο

Example9

968 g ε-caprolactone, 64 g of pentaerythritol and 0.12 g sulfuric acid (98%) were kept 18 hours under nitrogen at 12O ⁰ C for. The polymerization product was ^{cooled to 25 °} C. and analyzed. It had the following characteristics:

Hydroxyl number 103

Carboxyl number 6.5

Molecular weight 1930 ■

Example 10

97 g of ε-caprolactone, 3.1 g of liquid methylamine and 0.002 g of zinc chloride were placed in a 200 cm ^{3 autoclave.} The mixture was left to stand at 25 ° C for 2 days. The autoclave was then heated to 175 ° C. and held at that temperature for 30 hours. The mixture was then cooled to 25 ° C and the product analyzed. It had a hydroxyl number of 89 and a molecular weight of 615.

Example 11

In the same way as in Example 10, 97 g of ε-caprolactone with 3.1 g of ethylenediamine in The presence of 0.002 g of zinc chloride reacted. The product was a polyester with a hydroxyl number of 52.2 and a molecular weight of 2150.

Example 12

200 g of ε-caprolactone, 15 g of cellulose and 0.1 g of sulfuric acid (98%) were placed in a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser. The reaction mixture was ^{heated to 180 °} C. until it became semi-solid. After cooling, it was suspended in a mixture of acetone and methanol in a ratio of 7: 3 and centrifuged. The solid was ^{dried at 100 °} C. for 16 hours. 33 g of the end product were obtained.

Production of a saponified copolymer from ethylene and vinyl acetate

The boron trifluoride used is used in its etheratorm (47% BF ₃ ).

In a 12-1 three-necked glass reaction flask equipped with a stirrer, thermometer and distillation attachment, 1597 g of an ethylene-vinyl acetate copolymer (31.1% vinyl acetate) containing 5.76 mol of vinyl acetate and 51 n-butyl alcohol were added and 18.7 g of boron trifluoride given as an etherate. The mixture was heated to reflux temperature and 4890 cm ^{3 of} distillate were removed over a reaction time of 13 hours.

The reaction mixture was cooled with 41% n-butyl alcohol and 4.69 g of boron trifluoride were added. The solution was then refluxed again and poured into 7 hours 3930 ml of the distillate removed. This.

The procedure was repeated four times with 31 N-butyl alcohol each time and a total of 8.55 g of boron trifluoride. The reaction time was 25 hours, and a total of 12.0601 of the distillate was collected. The reaction mixture was at 160 ° C and 1 mm Hg distilled, leaving a very viscous, dark straw colored residue in the amount of 1351g (yield 99.7%) was obtained.

Hydroxyl number 184

Molecular weight 880 ^xo

% Vinyl acetate not converted 5.6

The combined distillates contained 4.65 moles of butyl acetate. The alcoholysis reaction was 81% complete.

Example 13

1000 g of the saponified copolymer obtained, which contained 23.6 g of boron trifluoride as an etherate with 47 percent by weight of BF ₃ , and 1500 g of an isomer mixture of Methyl-ε-caprolactone added. The mixture was then heated as follows: 1 hour at 100 ° C, 0.5 hours to 120 ⁰ C, 0.5 hours 14O ⁰ C and 1 hour at 165 ° C. The product was then distilled at 177 ° C. and 1 mm Hg, thereby obtaining 73 g of unreacted methyl caprolactone. The yield was 98%, the hydroxyl number was 80.5 and the molecular weight was 1,730.

Claims (1)

Claim: Process for the preparation of polyesters by polymerizing lactones in the presence of organic compounds and acidic inorganic compounds capable of opening the lactone ring Compounds as catalysts, characterized that one lactones of the general formula RCH - (CRg) »-C = O in which η is at least 4, R is a hydrogen atom or an alkyl, cycloalkyl, alkoxy or aryl radical, the total number of carbon atoms of the substituents R on the lactone ring not exceeding 12 and at least η + 2 of the radicals R being hydrogen atoms, in the presence polymerized from organic compounds with at least one hydroxyl or amino group and from sulfuric acid, phosphoric acid, hydrochloric acid, boron trifluoride or zinc chloride at temperatures of 20 to 180 ° C. Considered publications:
German patents nos. 926 758, 878 857,
609; German interpretative document K 17625 IVd / 39c (published on January 9, 1956); published documents of Belgian patent No. 534 967. A priority document was displayed when the registration was announced. 609 557/342 3.66 © Bundesdruckerei Berlin