DE1223555B - Process for the production of polymers and copolymers of diisopropenylbenzene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 c - 25/01

Number: 1223 555

File number: R 37344IV d / 39 c

Filing date: February 29, 1964

Opening day: August 25, 1966

The subject of patent application R 36081IV d / 39 c is a process for the production of polymers and copolymers of diisopropenylbenzene by polymerization in the presence of organolithium Compounds and polymerization accelerators, characterized in that as polymerization accelerators oxyalkylated monohydric mono- or polynuclear phenols and / or oxyalkylated polyvalent mono- or polynuclear phenols and / or polyglycols of the general formula

HIGH ₂ - (CH ₂ - O - CH ₂ ) ffl - CH ₂ OH

in which η is greater than 5, where the polyglycols can optionally be etherified with aliphatic monohydric or polyhydric alcohols or amino alcohols or esterified with organic acids.

According to this process, the polymerization is carried out at temperatures between -10 and + 50 ° C. In the production of polymers at temperatures below + 1O ⁰ C is observed depending on the amount of the accelerator and the catalyst used, an induction period, which is longer with falling temperature, so that also the reaction times are longer.

It has now been found that one can carry out the polymerization at lower temperatures than + 10 ⁰ C in unchanged or only slightly extended reaction times, if it initiates at temperatures above H- 1O ⁰ C and at a desired low temperature below + 10 ° C, e.g. B. - 50 ⁰ C, leads to the end, with otherwise unchanged conditions. With such a procedure, soluble and meltable products with better properties are obtained with, on average, even better yields than by the process of patent application R 36081 IVd / 39c.

For comparison, let the polymerization of p-diisopropenylbenzene with polyethylene glycol monocetyl ether according to the method described in the earlier patent application mentioned and the method according to the invention Working method listed.

I. I. Reaction Time
in yield K value He i II tempera
door hours % softening
Point ! ⁰ C 1.0 51.5 53.86 ⁰ C + 25 1.5 80.0 76.72 194 -20 192

Process for the production of polymers
and copolymers of the
Diisopropenylbenzene

Addition to registration: R 36081IV d / 39 c -
Interpretation document 1219 682

Applicant:

Rütgerswerke and tar recycling

Corporation,

Frankfurt / M., Mainzer Landstr. 195-217

Named as inventor:

Dr. Reinhard Bollwan, Letmathe (Sauerl.)

The polymerization is carried out in a reaction vessel provided with a stirrer with exclusion of air. You can now proceed according to two methods.

According to the first method, the solvent, accelerator and catalyst are presented and at about 15 ° C with a small amount of the monomer (s) added. After formation of a colored Complex, the reaction vessel is cooled to the desired temperature. During this cooling period the monomer or monomer mixture is allowed to continue to slowly drop in.

According to the second method, the entire amount of the monomer or monomer mixture can be used Submit including solvent and accelerator, add the catalyst at about 15 ° C and cool down to the desired reaction temperature after a colored complex has formed.

Further monomers can also be added at a later point in time, that is to say already at a correspondingly low temperature. The reaction solution slowly becomes more viscous during the cooling period. The average reaction time is I ¹ Z ₂ to 2 hours. After this reaction time, the product is precipitated in methanol to which a little acetic acid is added. The product is washed with methanol and dried at 30.degree. To 50.degree. C. in vacuo.

The yields are between 60 and 90%. The polymers are highly unsaturated. the Double bonds are very reactive. At increased

609 657/399

Claims (1)

3 4 At a higher temperature, the polymers can be heated with 0.6 parts of n-butyllithium (15% strength) and at 15 ° C Diisopropenyl content with crosslinking in the insoluble solution in hexane). - After inserting the borrowed state. The K-values reaction will bring the reaction solution to -18 ° C were cooled according to Fikentscher (cellulose chemistry. After one hour, 5 parts of styrene, 13 [1932], p. 58) in a 1% solution of the poly-5 dissolved in 25 parts of toluene, slowly added dropwise. To merisats determined in toluene. The softening points have a reaction time of 1.7 hours in total were determined on the Kofler heating bench. the viscous solution dilutes the polymer in metha nol precipitated and dried in vacuo at 40 ⁰ C. Example 1 43 parts of a colorless product are obtained. ίο softening point: 194 ° C; K value: 61.00. In a reac- composition of the polymer equipped with a stirrer:
tion vessel are 350 parts of toluene under nitrogen. 1.0 part polyethylene glycol monocetyl ether and 0.7 part I? * J, ⁰ ^ - Butyllithium (15% solution in hexane) mixed and ⁸⁷ ' ² > diisopropenylbenzene. 50 parts of p-diisopropenylbenzene were added at 15 ° C. 15th The reaction continues with strong discoloration of Example 5 Solution immediately. At the same time the reaction vessel will be described in a cooling bath within 20 minutes as in Example 1 are Stick-- 20 ⁰ C cooled and maintained at this temperature for a further material, 150 parts toluene, 1 part of polyglycol from MoI left 70 minutes. After a reaction time of 20 weight 6000 and 0.7 parts n-butyllithium (15% total 1 ^x / ₂ hours, the very viscous solution is dissolved in hexane). At 15 ⁰ C is diluted with methanol and the polymer was precipitated in adding dropwise a solution of 25 parts Diisopropenyl- in vacuo at 30 to 40 ° C dried. Benzene and 100 parts of toluene are started. After formation, 40 parts of a colorless product were obtained. the colored complex has a constant softening point: 192 ° C; K value: 76.72; Iodine number: 25 drops cooled to -18 ° C and the remainder of the solution was slowly added. 15 minutes after the end of the addition of Example 2, a solution of 25 parts of "-Methyl- styrene and 25 parts of toluene were slowly added. To As described in Example 1, with a total reaction time of 2 hours, the nitrogen is 200 parts of toluene, 1.0 part. diluted oxethylated solution, the polymer in methanol aus- / 3-naphthol and 1.0 part n-butyllithium (15% precipitated and ^{dried at 40 0} C in a vacuum. It solution in hexane). At 15 ° C., 32 parts of a colorless product are obtained with the. Dropwise addition of a solution of 50 parts of p-diisopropenyl softening point: 215 ° C .; K value: 48.0.
benzene and 150 parts of toluene started. According to the composition of the polymer:
Formation of the colored complex is under constant 35 _rr _ _{n /} ". ". Dropwise cooled to "-18 ⁰ C and the rest of the ^ 6.0% diisopropenylbenzene, Solution continued to be added slowly. After a ³⁴ '°' »« "methylstyrene. Response time of ₂ hours in total will be the. . . . Solution diluted, the polymer in methanol falls and ^{dried at 40 0} C in a vacuum. As described in Example 1 under, Stick-38 parts of a colorless product are obtained. material 150 parts of toluene, 1 part of polyethylene glycol mono Softening point: 202 ^° C .; K value: 73.1; Iodine number: stearate and 0.7 parts of n-butyllithium (15% solution 172 in hexane) dissolved. At 15 ° C is added dropwise Example 3 ^{e he} ™ solution of 45 parts of p-diisopropenylbenzene 45 and 100 parts of toluene started. After the formation of the As described in Example 1 under stick-colored complex, 300 parts of toluene and 45 parts of diisopropenylbenzene are cooled to -15 ° C. with constant dropping, and the remainder of the solution is added and 1 part of polyglycol with a molecular weight of 6000 is mixed dropwise. 40 minutes after the addition is complete and at 15 ° C., 0.6 part of n-butyllithium (15% strength is added to a solution of 5 parts of methyl methacrylate solution in hexane). After the 50 and 25 parts of toluene had been used, slowly added. After a reaction, the reaction solution is cooled to -15 ° C. reaction time of a total of I ¹ I _{2 hours.} After 30 minutes, 5 parts of methyl solution are diluted and the polymer is slowly precipitated in methanol pentadiene, dissolved in 25 parts of toluene, and ^{dried at 40 °} C. in a vacuum. There given. After a total reaction time of 40 parts of a colorless product. The reaction solution is diluted for 1.5 hours, the softening point: 190 ⁰ C; K value: 57.40.
Polymers precipitated in methanol and at 4O ⁰ C in the composition of the polymer:
Vacuum dried. There are 38 parts of a color- _{nA nn} , _n ·· > t- 1 loose product received. 94.0% p-diisopropenylbenzene, Softening point: 182 ° C; K value: 42.1. ⁶ > °° / o methyl methacrylate. Composition of the polymer: 60 96.0% diisopropenylbenzene, claim: 4.0% methylpentadiene. _{Further training of the} process for . ■ 1 λ position of polymers and copolymers ± $ for example 4 _{65 sates of} diisopropenylbenzene by polymer As described in Example 1, nitrogenation in the presence of organolithium compounds material 250 parts of toluene, 1 part of oxethylated cumyl bonds and oxyalkylated monovalent mono- or phenol and 45 parts of diisopropenylbenzene mixed polynuclear phenols and / or alkoxylated polynuclear 5 6 valuable mononuclear or polynuclear phenols and / or ethers or esterified with organic acids of polyglycols of the general formula can be used as polymerization accelerators HOCH ₂ - (CH ₂ -O-CH ₂ ), * - CH ₈ OH ^mäJ \ Ψ ^^ Τ ^ & ΛΛ} 7 ^Φ ί (German Auslegeschrift 1 219 682), thereby in which η is greater than 5, the polyglycols 5 being characterized in that the polymerization, if appropriate, with aliphatic one or more commences at temperatures above + 1O ⁰ C and Valuable alcohols or amino alcohols at temperatures below + 1O ⁰ C is continued. 609 657/399 8.66 © Bundesdruckerei Berlin