DE1184499B - Process for the production of copolymers from isobutyraldehyde and vinyl ethers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 08 g

German class: 39 c-19

Number: 1184499

File number: B 71209IV d / 39 c

Filing date: March 20, 1963

Opening day: December 31, 1964

It is known that aldehydes means acting ionic catalysts at temperatures below -10 ⁰ C in suitable solvents can be polymerized. Such polymers are unstable and already depolymerize at room temperature. At normal pressure they show no melting point, no thermoplastic properties and can only be deformed into brittle, glass-like bodies at high pressures, which are just as easy to depolymerize as the powdered products.

It is also known to combine formaldehyde or trioxane with vinyl ethers in the presence of ionic catalysts, such as boron fluoride to polymerize. The relatively unstable polymers des Polymerization with vinyl ethers makes formaldehyde much more stable against thermal effects Dismantling.

However, while the stabilization of polyformaldehyde is technically solved in various ways is a satisfactory stabilization of polyisobutyraldehyde and the preparation of stable copolymers of this aldehyde has not yet been achieved.

It has now been found that stable copolymers by polymerization of an aldehyde and vinyl ethers in non-protic organic solvents at temperatures below 0 ⁰ C in the presence of ionic catalysts are obtained when used as the aldehyde, isobutyraldehyde.

The process according to the invention gives thermoplastic copolymers which are comparable to polyvinyl ethers in terms of their thermal stability. The properties of the copolymers can be varied within wide limits through the choice of the reaction conditions and the type of vinyl ethers used. If the polymerization is started with isobutyraldehyde and then continued with vinyl isobutyl ethers, a polymer with a vinyl ether content of less than 5 percent by weight is obtained which is similar in its properties to polyisobutyraldehyde, but which is thermoplastic and has a melting range of 140 to 150 ⁰ C has.

One starts reverse the polymerization with isobutyl vinyl ether and continues with isobutyraldehyde, one already receives ° / ₀ elastomeric polymers at a Isobutyraldehydgehalt below 5 having a softening about 9O ⁰ C. With an increasing content of isobutyraldehyde in the polymer is continuously transition between elastomeric and pass through thermoplastic polymers. Particularly good thermoplastic processability and strength of the polymers are achieved with 20 to 40 percent by weight of isobutyraldehyde.

Process for the production of copolymers from isobutyraldehyde and vinyl ethers

Register ■■■; ■

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine ι

Named as inventor:

Dr. Eckhard Bonitz, Frankenthal (Palatinate);

Dr. Walter Scheidmeir, Ludwigshafen / Rhine -

In addition to this possibility, the proportion of the two components in the polymer by optional start to influence with one monomer and continuation of the polymerization with the other, Another way of working is that the two monomers are added periodically in pure form will. The amount of monomers added in the individual periods is the same or different be. The polymerization is preferably terminated with pure vinyl ether.

However, mixtures of the two monomers can also be added; these are either premixed or are only mixed in the reaction chamber. The mixing ratio of the two monomers can can be changed continuously or in discrete amounts during the polymerization. For example you start with pure isobutyraldehyde, add continuously increasing amounts of vinyl ether and finish the polymerization with pure vinyl ether.

The polymers of the same stoichiometric composition surprisingly have different properties, depending on whether they were prepared by adding the two monomers simultaneously or periodically in succession. Compared to those obtained under otherwise identical conditions but with simultaneous addition of the two monomers, the products prepared by periodic polymerization have a considerably greater stability than depolymerization in the presence of acids, a higher softening point and greater partial crystallinity. Even with thermal depolymerization at temperatures above 200 ° G, the two polymers show different behavior: The product obtained by adding the monomers at the same time largely splits into low-boiling compounds

409 760/416

bonds, the one represented by periodic polymerization mainly splits the aldehydic ones Components are removed and - without the use of foaming agents - foam-rubber-like forms are created Products of high stability and elasticity.

In addition to uniform vinyl ethers, mixtures of such ethers can also be used or but different vinyl ethers are periodically brought to copolymerization with isobutyraldehyde. As vinyl ethers z. B. isobutyl vinyl ether, methyl vinyl ether, ethyl vinyl ether and dipropyl methyl vinyl ether especially in question.

The polymerization is carried out with ionic catalysts, of which in particular Friedel-

Crafts catalysts and organoaluminum 15 formaldehyde
ties are preferred. Suitable Friedel deformability

Crafts catalysts are, for example, boron trifluoride, elongation at break

Aluminum trichloride, aluminum tribromide, titanium hardness

trachloride or boron trifluoride etherate. Also ethyl aluminum sesquichloride or methyl aluminum sesqui-isobutyraldehyde

Solvents at low temperatures in the presence of ionic catalysts was already known. But while this copolymerization, the properties of the homopolymers of formaldehyde can not change significantly, is surprisingly obtained from isobutyraldehyde and Vinyl ethers, such as vinyl isobutyl ether, copolymers with good properties, as from the following List shows:

Deformability.
Elongation at break.
hardness

Homopolymer
of the aldehyde

Well

48%
soft

bad

about 5%

brittle

Copolymer with vinyl isobutyl ether

Well
44%
soft _

very good

73%;

soft

chloride or phenylaluminum sesquichloride are available as
Suitable for polymerization initiators. The polymerization initiators are expediently used in amounts
from 0.001 to 1%> based on the amount of to
polymerizing monomers used. It is preferable to work with the solutions or suspensions of the polymerization initiators that are added
The beginning of or in the course of the interpolymerization reaction is added to the polymerization batch. The polymerization itself can be regulated to -80 ° C. both by the feed rate of a 0.5% strength boron trifluoride solution in hexane and by the addition rate of 750 parts to -70 ° C. within 45 minutes given chilled hexane. Then the. It is particularly advantageous to combine 80 parts of vinyl isobutyl ether and to use boron trifluoride and aluminum halogens to add the same amount of catalyst solution. When alkylene which simultaneously through separate feed streams ₃₅ precipitation with methanol, 95 parts of a finely added and only combined in the reaction vessel fluffy white polymer having a melting

The parts given in the examples are parts by weight and the percentages are percentages by weight.

Eg 1 I
80 parts of isobutyraldehyde are simultaneously with

will.

The ratio of isobutyraldehyde to vinyl ethers can be in a wide range between about 5 and 95% of each component can be varied.

The polymerization is conducted at temperatures below 0 ° C, preferably at -40 to -100 ⁰ C is performed.

Organic liquids are suitable as solvents for the polymerization reaction, which are not

40

point of about 143 ⁰ C obtained.
Example 2
47 parts of vinyl isobutyl ether are simultaneously with

Added 60 parts of a 0.1% Bortrifluoridiösung in hexane at -75 ⁰ C to 750 parts of gasoline within 45'Minuten and the polymerization was followed by addition of 80 parts of isobutyraldehyde

Are proton-active, preferably aliphatic carbons 45 and 75 parts of a 0.1% boron trifluoride solution in hydrogen, such as hexane, heptane, isooctane, cyclohexane. After treatment with methanol, hexane or methylcyclohexane, or halocarbons containing 2% anhydrous ammonia in solution, in the case of hydrogen or aliphatic ethers. Commercially available room temperature, 52 parts of a white, fine vinyl ether can generally be obtained for the polymerization of flaky polymer which can be used at 110 to without further purification. Technical 50 150 ° C melts, about 23% polyisobutyraldehyde ent-isobutyraldehyde with about 2 to 3% water is first held and can be pressed into films. The x-ray is dehydrated by azeotropic distillation. The advantages as interference charts of powder and film show running at 60.5 ⁰ C for continuous azeotropic mixture sawn partiellkristalline structures of PolyisobutyraldehydS is from 95% isobutyraldehyde and 5% water. The and the polyvinyl isobutyl ether. The foils are largely water-free. Distillation residue becomes clear and, without the addition of plasticizers, they have elasticity for several hours over calcium chloride or copper. The powdery product can be in sulphate, which acid components to be 220 to 24O ⁰ C, advantageously free exclusion of oxygen, to, dried and preferably foamed in Inertgasatmo- to a white highly elastic mass, sphere (eg., Nitrogen or argon) again destil- which has a much higher stability than traded. The aldehyde purified in this way is found in conventional foam rubber.
Inert gas atmosphere without stabilizer for a long time.

Periods constant and to the described Co- B e 1 s ρ 1 e 1 3

suitable for polymerization. A contamination of gasoline cooled to 750 parts to -75 ° C

Isobutyraldehyde with other aldehydes such as e.g. 25 parts vinyl isobutyl ether in 20 minutes n-Butyraldehyde in amounts up to a few percent 65 and at the same time 75 parts by weight of a 0.1% strength does not affect the copolymerization. · Added boron trifluoride solution in hexane. That kind of

The copolymerization of formaldehyde and vinyl-initiated polymerization is preceded by the addition isobutyl ether in non-proton-active organic 4 parts isobutyraldehyde within 10 minutes -

without further addition of catalyst - continued, and finally completed a 0, l% ig ^en boron trifluoride in 40 minutes after addition of further 48 parts of vinyl isobutyl ether and 110 parts. The rate at which the catalyst is added is continuously reduced. 83 parts of a white polymer with a polyisobutyraldehyde content of about 2% and a melting range of 87 to 95 ° C. are obtained. The X-ray interference diagram of powder and shows a partially crystalline structure.

B e ι s ρ ι e 1 4

75 parts of isobutyraldehyde are added simultaneously with 65 parts of a 1% Äthylaluminiumsesquichloridlösung in hexanes within 75 minutes 750Teilen to about -75 ⁰ C cooled gasoline and polymerization by the addition of 80 parts of vinyl isobutyl ether within an hour - without addition of further catalyst - continued. After a further hour, during which the reaction mixture maintained at -75 ° C, the reaction solution is poured into methanol of 20 ⁰ C. Here, 131 parts of a fine fluffy white polymer are eliminated, which does not melt up to 16O ⁰ C.

Heptane saturated with boron fluoride is added at the same time as 80 parts of isobutyraldehyde. Then 75 parts of methyl vinyl ether with the same amount of catalyst solution are added dropwise over a further 55 minutes. The reaction mixture is then allowed to warm to -10 ° C. and the mixture is added to ammonia gas ^: alkaline ^; made methanol. 148 parts of a white product precipitate which, in contrast to methylene polymerized with boron trifluoride

Foil io vinyl ether surprisingly in water, methanol and ethanol is insoluble. The product has one

■ "'■ Melting point of about 150 ⁰ C and has good compatibility with nitrocellulose jackets.

· ■ '■ " ^{ice cream} P ^ie10

160 parts of isobutyraldehyde are added simultaneously with 56 parts of a 1% ^en Äthylaluminiumsesquichloridlösung and 53 parts of a 0.1% boron trifluoride in hexane, which werdenj added dropwise separately over 170 minutes at -75 ° C to 750 Teäen gasoline. 40 parts of vinyl isobutyl ether are then added over the course of 45 minutes and, after a subsequent reaction time of 30 minutes, precipitated with methanol. Here, 181 parts emes white product are obtained with a melting point above 150 ^o Ci3iegenden. '.' ■. ',.:'. · '■■■ ..

The X-ray interference recordings show the ty * A pical picture of a copolymer of vinyl isobutyl ether and isobutyraldehyde with a high proportion

B e i s ρ 1 e 1 5

To 750 parts of -70 to 8O ⁰ C cooled gasoline
is given one after the other:
80 parts of isobutyraldehyde simultaneously with 75 parts of polyisobutyraldehyde.

a 1% ethylaluminum sesquichloride solution in hexane in the course of 30 minutes, 40 parts of vinyl isobutyl ether at the same time with 41.5 parts of a 1% strength

Ethyl aluminum sesquichloride solution in the course of 30 minutes, 40 parts of isobutyraldehyde with 65 parts Catalyst solution within 30 minutes, 40 parts Vinyl isobutyl ether simultaneously with 52 parts of the above Catalyst solution within 30 minutes. After a post-reaction time of

30 minutes-maintaining by the addition of methanol 40 only above 16O ⁰ C melting polymers

'R "" 1 Q

160 parts of isobutyraldehyde and 80 parts of vinyl isobutyl ether are simultaneously with 120 parts of a 1% Äthylduminiumsesqüicnloridlösung in hexane and 12 parts of a 0.1% ge (nr boron triflubride solution. in Hexane through / separate feeds within 150. Mir utes given to 750 parts of gasoline from - 4-75 ° C / after precipitation with methanol. ^ becomes 136 parts of a

₄₅

158 parts of a white, flaky polymer obtained, 90% of which dissolves in boiling hexane.'tier The residue of the hexane extract has a melting

range from 138 to 158 ⁰ C. '

^{B e} * ^s P ^{{ e l 6} to 750 parts of hexane at -75 to -80 ⁰ C within 126 minutes 320 parts of a mixture of 65% isobutyraldehyde and 35% vinyl isobutyl ether at the same time with 300 parts of a 0.1% boron fluoride solution in Hexane was added and the reaction continued at -70 to -75 ° C for an additional 90 minutes. After the reaction mixture has been introduced into the X-ray analysis shows the interferences of an isobutyraldehyde vinyl isobutyl ether polymer with a predominant proportion of polyisobutyraldehyde;

Example 10,. ;, · .., ·; ,

While cooling to -75 to -80 ° C, within added successively for 30 minutes to 750 parts of gasoline: 40 parts of vinyl isobutyl ether simultaneously with 37.5 parts of a 1% ethylaluminum sesquichloride solution in hexane and 37.5 parts a 0.1% boron trifluoride solution in hexane, 40 parts of isobutyraldehyde at the same time with 19 parts of each of the two Catalyst solutions, 40 parts vinyl isobutyl ether at the same time with 37 parts each of the two catalyst solutions, d l

4000 parts of methanol at room temperature in which

0.2 parts of anhydrous ammonia are dissolved, 55 40 parts of isobutyraldehyde fall simultaneously with 19 parts each 230 parts of a fine, flaky, white polymer with the two catalysts, 40 parts of vinyl isobutyl ether.

After precipitation with methanol, 53 parts of polymer product with a melting range of 140 to 142 ^° C. are obtained. The polymer contains about

their elasticity with films made of vinyl isobutyl ether 60 40% isobutyraldehyde and can be made crystal clear

a melting range of 121 to 151 ⁰ C and a polyvinyl ether content of about 10%. The product can be pressed into a crystal-clear film, which is in

is comparable, but has a ^{softening point 40 to 70 0} C higher than a film made of polyisobutyl vinyl ether produced under conventional reaction conditions.

Example 7

To 750 parts from -75 to
Heptane will be within

-8O ⁰ C cooled 55 minutes compress 75 parts films.

Example 11

^{Isobutyraldehyde and vinyl isobutyl ether} are added to 750 parts of benzene cooled ^{to -70 to -8O 0} C in the following sequences:

72 parts of isobutyraldehyde simultaneously with 100 parts of a 1% ^en in Äthylaluminiumsesquichloridlösung

Hexane and 100 parts of a 0.1 ° / ^s oig Borfluoridlösung in hexane over 50 minutes, 8 parts of vinyl isobutyl ether lOOTeilen simultaneously with 11 parts of the two catalysts within 10 minutes, 72 parts of isobutyraldehyde with each of the two catalyst solutions £ within 50 minutes , 8 parts of vinyl isobutyl ether with 11 parts each of the two catalyst solutions within 10 minutes and finally 40 parts of vinyl isobutyl ether. This gives a fine flaky polymer 182 parts, which ao melts between 145 and 16O ⁰ C and contains a high proportion of Polyisobutyraldehyd.

Example 12

Cooled to 700 parts to about -75 ⁰ C petrol * 5 vinyl isobutyl ether are added and isobutyraldehyde in the following sequences:

72 parts of vinyl isobutyl ether simultaneously with 10 parts of a 1% strength ethylaluminum sesquichloride solution in hexane and 10 parts of a 0.1% boron trifluoride solution in hexane within 50 minutes, 8 parts of isobutyraldehyde simultaneously with 11 parts each of the two catalyst solutions used above within 10 Minutes, 72 parts of vinyl isobutyl ether simultaneously with 100 parts of each of the two catalyst solutions in 50 minutes, 8 parts of isobutyraldehyde simultaneously with 11 parts of each of the two catalyst solutions, 40 parts of vinyl isobutyl ether within 30 minutes without adding any further catalyst. After precipitation in methanol, 198 parts are obtained of a colorless rubber-like product having a melting range of 48 to 6O ⁰ C and a Isobutyraldehydanteil of about 8%.

Example 13 “.

To 750 parts gasoline cooled to about -75 ° C are given within 30 minutes each:

40 parts of vinyl isobutyl ether at the same time with 53 parts of a 1% is ^en ethylaluminum sesquichloride solution in hexane and 53 parts of a 0.1% boron fluoride solution in hexane, 40 parts of isobutyraldehyde at the same time with 53 parts of each of the two catalyst solutions used above, 40 parts of vinyl isobutyl ether at the same time with 53 parts each of the two catalyst solutions, 40 parts of isobutyraldehyde at the same time with 53 parts of each of the two catalyst solutions, 40 parts of vinyl isobutyl ether, 22 parts of a 1% strength ethylaluminum sesquichloride solution in hexane at the same time as 22 parts of a 0.1% strength boron trifluoride solution in hexane. The polymer obtained has a melting range of 88.5 to 92 ° C., is thermoplastic and contains about 8% polyisobutyraldehyde. The yield is 131 parts.

Example 14

The polymerization reaction is carried out analogously to Example 11 by adding the two alternately Monomers carried out; only 40 parts of isobutyraldehyde are used. After failing in Methanol are 136 parts of a white, finely flaky, obtained soft polymers with a polyisobutyraldehyde content of about 15%.

B ei s ρ i e 1 15

To 750 parts of heptane, which are cooled to -75 to -8O ⁰ C, 240 parts of a 0, l% aqueous Borfluoridlösung and 320 parts are a mixture of equal parts of isobutyraldehyde and methyl vinyl ether were added dropwise through separate inlets at the same time within 130 minutes. The reaction mixture is heated to -40 to -50 ° C. within 10 minutes, while stirring, and the gel-like product is poured into ammoniacal methanol. 142 parts of a white polymer with a softening range between 70 and 130 ^° C., which is insoluble in water, methanol, ethanol and isobutanol, are obtained.

Claims (1)

Claim: A process for preparing copolymers by polymerization of an aldehyde and vinyl ethers in non-protic organic solvents at temperatures below 0 ⁰ C in the presence of ionic catalysts, characterized in that there is used as the aldehyde, isobutyraldehyde. Considered publications: U.S. Patent No. 3,076,786. 409 760/416 12.64 Q Bundesdruckerei Berlin