SU834001A1 - Method of preparing unsaturated polyester resins - Google Patents

Description

(54) A METHOD FOR OBTAINING NONSATURATED POLYESTER

RESIN

when at 14 the polyester is a solid or highly organic product. In such cases, it is necessary to drain the polyester at high temperature, cool it, grind it and only then combine it with the monomer. When using the indicated stabilizing system, the stability of polyester resins and the duration of the process for their preparation are not long enough.

The purpose of the invention is to increase the stability of polyester resins, simplify the process and shorten the process time.

The goal is achieved by the fact that in the method of obtaining unsaturated polyester resins by polycondensation of polyatomic alcohols or derivatives of polyhydric phenol derivatives with a mixture of unsaturated polybasic acids or / and their anhydrides at 150-250s followed by the interaction of the obtained resin with unsaturated mono (olig) in the presence of as a stabilizing system, a mixture of diphenylolpropane and / or propane-2,2 4-oxyphenyl-4- (oxipropoxyphenyl.) Ja, hydroquinone and copper salts of naphthenic or fatty acids a row with the next content of the components of the stabilizing system in relation to the total amount of polyester resin and unsaturated mono (oligo) measure, ve, p.%:.

0.01-0.5

Diphenyl alpropane

Propane-2, 2 4-hydroxyphenyl-4- (hydroxypropoxyphenyl)

0.01-1.2 0.005-0.025

Hydroquinone

Naphthenic or Copper Salts

.0,001-0,01

. fatty acids and the interaction of the polyester resin and the mono (oligo) measure is carried out at 140-200 ° C.

Hydroquinone (GC) is taken in an amount of from 0.005 to 0.025 wt.%, Preferably from 0.01 to 0.02 wt.%, And is introduced before combining into the polyester at the end of the polycondensation process.

Diphenylopropane (DFP) is taken in the amount of from 0.01 to 0.5 wt.%, Before | 1Relatively from 0.02 to 0.1 weight. diphenylolpropane monoester and propylene oxide in an amount of from 0.01 to 1.2 wt.%, preferably from 0.02 to 1.0 wt.%. These components of the stabilizing system are introduced into the polyester after or during the polycondensation process.

Copper salts (NM) of naphthenic or fatty acids are introduced into the monomer as a solution in the same monomer in an amount of from 0.001 to 0.01 wt.%.

preferably from 0.002 to 0.005 wt.%. After the naphthenic or fatty acid copper salts have been added, the monomer can be preheated before the polyester is introduced into it.

The proposed process for producing unsaturated polyester resins is carried out by polycondensation of monohydric alcohols or polyatomic phenols with a mixture of unsaturated and saturated polybasic acids or their

anhydrides at 150-250 ° C to an acid number of 70-10 mg KOH / g resin. Upon reaching the specified acid number, hydroquinone, diphenylolpropane and / or monoester of diphenylolpropane and propylene oxide (MEDFP) are introduced into the reaction mixture, if necessary, the reaction mixture is cooled to a temperature not higher than and heated at this temperature with preheated to a temperature not higher than monomer containing dissolved copper salt.

As the starting alcohol components, any of the polyhydric alcohols may be used alone or in a mixture with each other such as ethylene glycol, picol, propylene glycol, diethylene glycol, glycerin, oxypropylated diphenylolpropane, polyoxyethylene glycol, polyoxypropylene glycol, and the like. It is preferable to use a dihydric alcohol or derivatives of a diatomic phenol, although small amounts of higher polyhydric alcohols can also be used.

As acidic components, mixtures of unsaturated and saturated, polybasic acids and / or their anhydrides can be used (unsaturated - such as maleic, fumaric itaconic, etc., saturated - phthalic, tetrachlorophthalic, adipic, sebacin and others). These modifying acids or their anhydrides can be used alone or in mixture with each other.

The ratio of alcohol and acid components is 1.051, 25: 1 mol.

As a polymerizable monomer, liquid monomer such as styrene or alkyl- or halo-substituted styrenes, methyl methacrylate, acrylonitrile, oligoether acrylates can be used. and etc.

Modifying additives such as rosin, castor oil, etc. can also be added to the initial mixture.

The initiator of curing, which is introduced into the polyester compositions, containing hydroquinone and diphenylolpropane or the monoester of diphenylolpropane and propylene oxide in combination with copper salts of naphthenic or fatty acids, can be any initiator

: peroxide or hydroperoxide type of those commonly used for curing unsaturated polyester resins.

Conventional cobalt or amine accelerators can be used as accelerators.

Example 1. 500 g 1 (1.1 mol) of oxypropylated diphenylolpropane and 129.6 g (1.0 mol of maleic anhydride) are loaded into the reactor; equipped with a stirrer, a thermometer and a fridge, and 129.6 g (1.0 mol of maleic anhydride). . To a current of nitrogen up to 751, turn on the stirrer and then for 1.5-2 hours the temperature is raised to 20 ° C ± 5 ° C and the process is conducted at this temperature.

to produce a product with an acid number of 10-15 mg KOH / g.

The resulting product is combined with styrene at the rate of obtaining a resin with a styrene content of 44-46% (chemical resistant polyester resin of the type PN-15). The combination is carried out at a temperature of polyester 190-200 0 in the presence of various stabilizing systems. The effectiveness of stabilizing systems is evaluated by the viability of polyester resins, i.e. the time during which the resin: maintains fluidity at a given temperature. The effect of various stabilizing systems on the stability of 5 unsaturated polyesters of the type PN-15, estimated by the viability of polyester resins, is shown in Table 1.

Table 1

190-200

190-200

190-200

190-200

190-200

190-200

190-200

190-200

190-200

0.02

Resin gela 20 GC tinized when combining

0.02

Also

0-70 GC. FC OD

  "

15

ten

15

400

80

. Phosphoric acid The final product (experiments 8-16, Table 1) is a clear yellow liquid and has the following characteristics:

Density at, g / cm Dynamic viscosity at 2Т) ° С, cPz Monomer content,% Gelation time in the presence of 8% NKi accelerator 3% isopropylbenzene hydroperoxide at, min Acid number, mg KOH / g

8340018

Continued table.

Example 2. In a reactor equipped with a stirrer, a thermometer and a refrigerator load 429.1 g

(1.04 mol) of hydroxypropylated diphenylpropane, 144 g (0.06 mol) of polyoxypropylene glycol-2002 (molecular weight 2000, rhodroxyl number 1.50-1.72%) and 117.6 g (1.0 mol)

maleic anhydride. Reactionary

the mixture is heated for 0.5 h in a stream of nitrogen to 75 1, turn on the stirrer and within 1.5-2 h raise the temperature to 200 ± 5 s. At this temperature, the process is carried out to obtain a product with an acid number of 10-15 mg KOH / G. The resulting product is combined with styrene at the rate of obtaining a resin with a styrene content of 39-41% (chemical-resistant polyester resin PN-16). The combination is carried out at

polyester temperature of 190-20 (3 ° and 140-150 C in the presence of various stabilizing systems. The effectiveness of stabilizing systems is evaluated by the viability of polyester resins, i.e. by time, during

190-200

60-70

2

190-200

(Known60-70 Ny) 190-200

70-80

190-200

190-200

70-80

70-80

190-200

70-80

190-200

190-200

70-80

70-80

190-200

whose resin retains fluidity at a given temperature. The effect of different stabilizing systems on the stability of unsaturated polyester resins, assessed by their viability when shown, is shown in Table 2.

Table

The final product (experiments 4-11, Table 2) is a clear yellow liquid with the following indicators:

Density at

1,032-1,044

g / cm

Dynamic viscosity at 2Q ° Cf

920-1210

spz

The content of monome99, 0-40,2 ra,

Gelatinization time in the presence of

8% accelerator NK-1

and 3% hydroperoxide

isopropyl benzene

at, min

120-160

Acid number,

6.0-9.0

mg KOH / H.

Example 3. In a reactor equipped with a stirrer, a thermometer and a refrigerator, load 504.6 g

60-70 GC FC

190-200 70-80 DFP 190-200

70-80

190-200

Continued table. 2

(1.1 mol) of diethylene glycol, g (0.67 mol) of maleic anhydride and 212.9 g (0.33 mol) of ftaS of left anhydride, give a stream of nitrogen and raise the temperature to 120 ° C over 1 hour. At this temperature they give an exposure of 1 hour, after which the temperature in the reactor is raised to 200-220 0 for 4-6 hours and the process is carried out at this temperature until a product with an acid number of 25-40 mg KOH / G is obtained. The resulting product is combined with styrene at the rate of obtaining a resin with a styrene content of 30-33% (general purpose resin type PN-1). Combination with styrene and evaluation of the effectiveness of various stabilizing systems are carried out according to the procedures described in Example 1. The effect of various stabilizing systems on the stability of the products obtained is shown in Table 3. T and blitz 3

0.02

Also

0.1

0.5

360

0.025

0.01

NM DFP

60

0.01

0,005 GC NM

0.001

13

The final product (tests 3-9, table 3) is a clear yellow liquid and has the following characteristics:

Density at 20 C, g / cm

Conditional viscosity according to VZ-1 viscometer at, 0

183400114

Continued table. 3

Monomer content,% 30.2-32.2 Gelation time at 20c in the presence of 3% isopropylbenzene hydroperoxide and 8% of IR-1 accelerator, min 70-120 Example 4. In a reactor equipped with a stirrer, a thermometer and a refrigerator, load 377.1 g (1.1 mol) of ethylene glycol, 342.5 g (0.65 mol) of maleic anhydride and 280.4 g (0.35 mol) of 4 talic anhydride, give a stream of nitrogen and within 1 hour raise the temperature to 120 ° C, at this temperature, they give an exposure of 1 h, after which the temperature in the reactor is raised to 200–220 s for 4–6 h and the process is carried out at this temperature to obtain a product with acid by the number of 42-47 mg KOH / g. The resulting product is combined with

oligoester TGM-3 (triethylene glycol dimethacrylate) at the rate of obtaining a resin with an oligoester content of 55-60% (general purpose resin of type OPS-609-21M). The combination with the oligoester and the evaluation of the effectiveness of the action of various stabilizing systems are carried out analogously to Example 1. The effect of various stabilizing systems on the stability of unsaturated polyesters of the type NPS-609-21M, estimated by the viability of

resins at 13 (f With shown in table. 4.

I,. Table 4

The final product {experiments 2-8, Table 4) is a clear greenish-brown liquid and has the following characteristics:

Density at 20 ° C, g / cm

1,165-1,180

Conditional viscosity according to VZ-1 viscometer at 20 ° C, s

22-35 Gel time in the presence of 3% isopropyl benzene hydroperoxide and 8% accelerator NK-1

. at 20–5-18 h

at 70 ° С15-30 min

Example 5. In a reactor equipped with a stirrer, a thermometer and a refrigerator, 194 g (1.1 mol of diethylene glycol, 102 g {0.45 mol) maleic and 115.75 g (0.3 mol) methyltetrahydrophthalic anhydrides 85 g {0, 25 mol) adipic acid

(Known) 190-200

190-200

190-200

190-200

190-200

190-200

3.25 g {0.01 mol) melamine give a stream of nitrogen and raise the temperature for 2 hours, then increase the temperature to 1.5 ° C for 1.5 hours and continue to process

product with an acid number of 25-20 mg KOH / g. The resulting product is combined with oligoester MGF-9 {dimethacrylate bis-triethylene glycol-phthalate) in a weight ratio of 1: 4, the mixture after

0 combining was added accelerator K-1 (solution of cobalt bis-n-butyl phthalate in TGM-3 oligoester with an active cobalt content of 1.5%) in an amount of 3% by weight of the resin (polyester

5 electrical insulation compound type KP-50). The combination with the oligoester and the evaluation of the effectiveness of the action of various stabilizing systems are carried out analogously to example 1. -Effect

0 different stabilizing systems on the stability of unsaturated polyesters of the type of electrical insulating compound KP-50, estimated by the viability of polyester resins with, are shown in Table 5.

five

Table 5

60-70

70-80

70-80

70-80

70-80

70-80

190-200

190-200

The final product (experiments 2-8, table 5) is a single-layer transparent liquid that does not contain extraneous inclusions and has the following indicators: Viscosity by VZ-4 viscometer at 20 ± 0.5 ° C, C 120-160 Drying time thick layer at 125 ±, min 4-10 Duration of drying in a thin i layer at 125 ± 2 ° С,

min 3-8

Cementing ability, kg

at 20 ± 28-37 at 155 ± 2 ° С 20-32 Specific volumetric electric co. resistance, ohm-cm.,. Loading

raw material

Heating up to operating temperature

Continued table. five

х.ь -L--.- 4.10 -2,3-10 „at 155 ± 2 ° С 7,, 2 10 after 24 hours in an atmosphere with a relative humidity of 95 ± 2% at

4.7-, 6- 20 ± 2С

electrician

rochnost, kV / mm at 15-35 ° С

28-38 after 24 hours in the atmosphere with a relative humidity of 95 ± 2%

at

25-34

A comparative characteristic of the duration of the production cycle of various grades of unsaturated polyester resins by known and proposed methods is given in Table 6.

Table

18

18

18

20

eight

 Since, at 130-140s, the unsuitable PN-15 is a highly viscous mass, drainage is carried out at 160-180 ° C, after which the resin is cooled to a temperature not higher than bc, is crushed and loaded into the apparatus for combining with styrene.

Claims (1)

1. Goldberg M.M. Materials for 3. USSR author's certificate of paint and varnish coatings, M., Himi, No. 478031, cl. C 08 G 63/52, 1975. 1972, p. 115. (prototype).