JPS5821617B2 - Polycarbamate ino Seizouhou - Google Patents

Description

Detailed Description of the Invention The present invention relates to a new method for producing polycarbamates that can be used in paints, adhesives, fiber treatment agents, plastic molded products, agricultural chemicals, pharmaceuticals, etc. Carbamates have long been equivalent to urea. It was made with alcohol and more.

However, since this reaction is reversible, the desired product can only be obtained if there is an excess of alcohol.This method uses an excess of raw material alcohol, so it is necessary to separate and purify the reaction product, and remove unreacted alcohol. Recovery, etc. will be subject to considerable technical and economic constraints.

Furthermore, with this method, it is almost impossible to treat polyhydroxy compounds having divalent or higher hydroxyl groups.

Although it is an experimental method for converting complex compounds having divalent or higher hydroxyl groups into polycarbamates, chlorocarbonate of corresponding polyhydroxy compounds, phosgene compounds,
There is no choice but to use chloroformate or the like.

However, since all of these are easily decomposed and dangerous, they can only be applied to the production of limited polycarbamates.

In this regard, the method proposed by W. M. Kraft (J. A. C.
,S.

Vol. 70, p. 3569), it is easily available as a raw material,
Moreover, it is advantageous to use alkyl carbamates which are stable and highly safe, but not only is the catalyst used AI (OCa R7) 3 which easily decomposes and is difficult to handle, but the reaction time is over 15 hours. The disadvantage is that it requires a long time.

The present invention uses a tin compound as a catalyst to polycarbamate a polyhydroxy compound and a carbamyl group-containing compound (
Hereinafter, this will simply be referred to as a reaction.

) to produce polycarbamates.

According to the method of the present invention, the desired polycarbamates can be produced in a high yield in an extremely short time of 2 to 3 hours.

The reaction temperature is preferably 100°C or higher, usually 110 to 130°C, in order to remove the lower alcohol produced.
Use the range of

The amount of catalyst used should normally be 0.1% or more.

Tin compounds used as catalysts include tin logenide and metal salts of organic acids, and specific examples include 5nC1.
4, S n B r 4, S n I 4, S
n C12, SnBr2, SnI2, tin acetate, tin octylate, silver stearate, and the like.

Another effective catalyst is an organotin □ compound represented by the following general formula.

R35nO2CR', R2Sn (02CRS2, R2S n (OR') 2, R35nOR', R25nX2, R35nX.

[However, R and R/ are the same or different C1-12 alkyl group, aryl group, cycloalkyl group, ara.

represents a rukyl group, and X represents...a rogen atom or a hydroxyl group.

] Organotin compounds represented by the above general formula include, for example, dimethyltin dibromoacetate, dimethyltin ditrichloroacetate, and dimethyltin dibene.

Shade, dibutyltin diacetate, dimethyltin civalate, dimethyltin oxalate, dimethyltin phthalate, dimethyltin succinate, dibutyltin acetate, dibutyltin oxalate, dibutyltin phthalate, dibutyltin sebacate, dibutyltin thiomalate , dibutyltin acetate, dibutyltin ethyl malonate, dibutyltin oxalate, dibutyltin malate, dibenzyltin diacetate, dibenzyltin dilaurate, dibenzyltin distearate,
Diphenyloctyltin acetate, tribenzyltin acetate, tribenzyltin stearate, tributyltin anoacetate, triphenyltin laurate, triphenyltin acetate, triphenyltin benzoate, dimethyltin diacetate, dimethyltin dilaurate, dibutyltin diacetate, Dibutyltin dilaurate, dibutyltin dibenzoate, dibutyltin malate, diphenyltin diacetate, dibenzyltin dilaurate, diphenyltin di2-ethylhexanoate, trimethyltin acetate, tributyltin laurate, tributyltin benzoate, trioctyltin laurate, Trioctyltin cyclohexanoate, dibutyltin dichloride, dioctyltin dibromide, dimethyltin iodide, diphenyltin dichloride, tetrabutyl-1,3-diacetyloxydistanoxane, tetrapropyl-1-chlor-3
-Hydroxydistanoxane, tetrapropyl-1, 3
-Diglopoxydistanoxane, 1,1-diptyl-3
- 3-dipropyl-1-hydroxy-3-acetyloxydistanoxane, dibutyltin dichloride, dibutyltin dichloride, dibutyltin dichloride, diphenyltin digropoxide, triphenyltin methoxide, etc.

For a more detailed example, see Chem, Rev., 60.4.
59 (1960, Ingham et al.)
It is also described in Japanese Patent Publication No. 43-9211.

When reacting a polyhydroxy compound and a carbamyl group-containing compound using such a catalyst, a solvent is not required, but a hydrocarbon solvent or other suitable solvent may be used at one time. .

As the polyhydroxy compound, any compound having a hydroxyl group can be used without any restriction3, and any compound having a molecular weight can be used.

There are various types of low molecular weight polyhydroxy compounds including alkyl, aryl, aralkyl, and cycloalkyl compounds.

Specific examples include ethylene glycol, 1,4-butanediol, 1,12-dodecanediol, glycerin,
Trimethylolpropane, pentaerythritol, 2-
7 Chlorhexylpropanediol, xylylene glycol, butylmercaptophenylpropanediol, bisphenol A1 tetrabromobisphenol A1 catechol, xylenol, propylene glycol, diethylene glycol, triethylene glycol, 2-ethyl-1,3-hexanediol, tris( 2-hydroxyethyl) isocyanurate, 2,2-dimethylpropanediol, methylpropylpropanediol, 1,3-
Examples include butanediol, sodium inosinate, xylose, norpit, and the like.

High molecular weight polyhydroxy compounds include, for example, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., condensates of formaldehyde with phenol, cresol, etc., and the above-mentioned low molecular weight polyhydroxy compounds and polybasic acids. , polyester polyol or alkyd resin having a hydroxyl group, which is a condensation product with its anhydride or its lower alkyl ester as the main raw material, vinyl acetate (co-)
Partially saponified polymers, (co)polymers of allyl alcohol, (co)polymers of hydroxyalkyl (meth)acrylates
Examples include hydroxyl group-containing (co)polymers such as polymers.

Polybasic acids that are raw materials for the above-mentioned polyester polyols and alkyd resins include co-phosphoric acid, maleic acid,
Adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, azelaic acid, phthalic acid, trimellitic acid, pyromellitic acid, cyclopentane-1,2-dicarboxylic acid, 4
-Methylhexane-1,2-dicarboxylic acid, cyclohexane-2-dicarboxylic acid, p-chlorophthalic acid, tetrabromophthalic acid, methylsuccinic acid and the like.

As the carbamyl group-containing compound to be reacted with these polyhydroxy compounds, any general-purpose compound can be used, but in particular, compounds having 1 to 4 carbon atoms such as methyl carbamate, ethyl carbamate, or n-butyl carbamate. Alkyl carbamates having alcohol as the ester-forming component are suitable.

The reaction between the polyhydroxy compound and the carbamyl group-containing compound in the method of the present invention is called a transesterification reaction, and is carried out by polycarbamate formation such as transesterification.

The present invention will be explained below according to examples.

"Parts" and "%" in the text indicate parts by weight and % by weight.Example 1 Ethylene glycol 31.0 parts (0
, 5 mol) Ethyl carbamate 89.1 parts (
1.0 mol) dibutyltin dilaurate 0.2 parts xylene 250 parts to 500 r
The mixture was placed in a rLl Niro round bottom flask, and a packed column equipped with a reflux ratio regulator was attached to the top for reflux.

(Inner temperature 120-130°C). During this time, the tower top temperature was 60~
Add ethanol while adjusting the reflux ratio to 80°C.
The xylene azeotrope was distilled off.

After 2 hours, it was confirmed by gas chromatography that the removal of ethanol had been completed.

After cooling, the precipitated crystals were separated and recrystallized from ethanol.

Yield after recrystallization: 57.7 parts (78%), mp. 164-1
66℃.

By analyzing this crystal, it was confirmed that it was a corresponding ethylene biscarbamate.

Examples 2 to 8 Table 1 shows the results of the same procedure as in Example 1 except that the same amount of tin compound was used instead of dibutyltin dilaurate.

was treated as in Example 1 and then heated under reduced pressure to remove the xylene, yielding the corresponding biscarbamate which is a viscous liquid at room temperature.

Yield 119.5 parts (88%) Example 10 Hexamethylene glycol 59.1 parts (0
, 5 mol) n-butyl carbamate 117.2 parts (
0.2 parts of tin octylate (1.0 mol) was treated in the same manner as in Example 1, and the solidified product was recrystallized from dimethylformamide-ethanol (1/1).

Yield after recrystallization: 83.7 parts (82%) mp, 183.5
~187℃.

Analysis confirmed that it was hexamethylene biscarbamate.

Example 11 p-xylylene glycol 50.0 parts Ethyl carbamate 64.5 parts trioctyltin acetate 0.2 part xylene
After 250 parts were treated in the same manner as in Example 1, the resulting crystals were filtered and recrystallized from dimethylformamide-ethanol (1/1).

Yield after recrystallization: 69.0 parts (85%) mp, 208~
211℃.

The analysis results confirmed that it was p-xylene biscarbamate.

Example 12 Bisphenol A 57.1 parts (0.25 mol) Ethyl carbamate 44.6 parts (0.25 mol)
, 5 moles) 0.2 parts of diphenyltin dichloride and 250 parts of toluene were treated in the same manner as in Example 1, and the resulting crystals were separated and recrystallized from ethanol-dimethylformamide (1/1).

Yield: 58.0 parts (81%) mp201-204°C.

Analysis confirmed that it was the corresponding biscarbamate.

Example 13 Polyester* 81.6 parts Ethyl carbamate 44.6 parts Tetrabutyl-1,3-diacetoxy 0.2 parts Cydistanoxane xylene 200 parts* 1.
4-butanediol 45.1 parts, adipic acid 36.5 parts
A polyester with a hydroxyl group at the end synthesized from

After treatment as in Example 1, a solidified product was obtained.

Analysis of the product yielded 88.1 parts (90%) revealed that there were no hydroxyl groups and only carbamate groups were present.

Example 14 Acrylic resin containing hydroxyl group* 94.0 parts Ethyl carbamate 44.6 parts Tin chloride
0.2 parts toluene
250 parts *2 Acrylic resin having hydroxyl groups in side chains polymerized from 130.4 parts of hydroxyethyl methacrylate, 104.2 parts of styrene, and 142.2 parts of n-butyl methacrylate.

was treated in the same manner as in Example 1, and the solidified product was filtered and dried.

Analysis of the 110P (94%) product showed that there were no remaining OH groups, only carbamate groups.

Claims (1)

[Claims] 1. A method in which a tin compound is used as a catalyst when producing polycarbamates by converting a polyhydroxy compound and an N-unsubstituted albamyl group-containing compound into polycarbamates.