SU1065426A1 - Process for preparing oligomers with acrylate end groups - Google Patents

Abstract

A METHOD FOR OBTAINING OLIGOMERS WITH END ACRYLATE GROUPS by interacting a hydrocarbon with functional end loops with an addition agent in an organic solvent medium. characterized in that, in order to improve the physicomechanical properties of vulcanizates containing the target product, diLithioligo is used as a hydrogen with functional end groups; a diene of the general formula E Zi - (- CH2-C- (JH- (where R is H, CHj, p 21-187, and the reaction process is carried out by treating dilithium oligodiene with 1.0-3.3 mol of ethylene oxide per 1 mol of active lithium followed by the introduction of acrylic or methacrylic acid into the i reaction mixture, the process being carried out at a molar ratio of ethylene oxide and acrylic or methacrylic acid hdoranhydride

Description

O5

ate

42

to

about

The invention relates to a method for producing oligomers with terminal (meth) acryl groups and can be used in the petrochemical industry, and the resulting

СНг СН2 С- 1-0-1H2-Ш20-С-0-В-0-С -OCHjoligomers - as components in vulcanizing mixtures.

Known oligomers with terminal acrylate groups of the formula

Н5 СНг- 0-С- С-CHg, (JH2 С-С-О - Шг-Ш2- {СН2- (1Н СНCH igg СНа-CHg-О-С-С ОН 2 о JH, Example 2.K to solution 300 g of oligobia tadienyl diliti with M - 10100 (p 187) and with keeping the active lithium of 0.0594 g-eq in 2500 ml of gasoline, 10 ml of ethylene oxide {8.8 g or 0.2 mol) are added with stirring. the ratio to active lithium is 3.3. After 10 minutes, 5.4 (0.059 mol) of acrylic acid chloride are added. After processing as in Example 1, 303 g of a viscous oligomer with M p - 10 250 and content of acrylate groups 0 are obtained. , 2010 3 g-eq / g Example 3. To a solution of 150 g of opigoiso prenidylity with Mr - 1420 (p 21) and lithium active content 0.221 g-eq in 1500 ml of gasoline with stirring, pour in 22 ml of ethylene oxide (19.4 g or 0.44 mol). The molar ratio to active lithium is 2: 1. After 10 min, the solution is treated with 23.1 g ( 0.221 mol) -methacrylate acid acid: 152 g of a viscous oligomer with X 1600 are separated in the same way as described in Example 1. With stirring, 47 g (1.07 mol) of ethylene oxide (molar ratio to active lithium 1: 1) are added with stirring, after 10 min the solution is processed Pipeline 111 g (1.06 mol) of chloro acid anhydride metakrylovoy. As described in example 1, 4280 g of oligomer with Mn-8300 is isolated. The product has a structure similar to that obtained in example 1, with an average degree of polymerization of 150. Opigodienacrylates are the temperature of non viscous liquids, 250 ° C, while as observed up to T for methacrylates of higher alcohols 2, the flash point is 100-120 ° C, so the use of the proposed oligodien acrylates improves fire safety in the preparation of vulcanizates. Applying the obtained oligodienediacrylate as components of rubber mixtures leads to an improvement in the technological properties of the rubber mixture and to an increase in the physicomechanical properties of vulcanizates. In tab. Figure 1 shows a comparison of the properties of non-rubber rubbers with the introduction of the proposed additives and the known oligo ether acrylates into the composition of the volcano. The composition of the investigated compositions, parts by weight; control mixture: SKN-40 Stearic acid Zinc oxide Sulfamide 1.0 Sulfur 2.0 The mixture of the prototype contains an additional 3 wt.h. methacrylic ester alcohol fraction C. ,,, and 1.0 May. including oligobutylene with M f, - 2500. Vulcanization at 153 ° C for 30 minutes. In tab. 2 presents a comparison of the main characteristics of the vulcanizer on the basis of the SKI-3, modified OBDL - MA, with the characteristics of the vulcanizates of the prototype. The composition of the initial mixture, May. hours, without modifiers: SKI-3100 Soot TM-5020 Zinc oxide5 Stearic acid Santokur Cera2 Mixtures modified by OBDL-MA, as can be seen from the table. 2, have advantages in hardness, in resistance to multiple stretching. The best composition of the prototype (Example 6) allows to obtain a similar result on the resistance to multiple stretching, however, in this case, the number of input known oligoester acrylates reaches 62% (against 30 in the proposed one). In tab. 3 presents a comparison of the main characteristics of vulcanizates based on SKN-40, modified OBDL-MA, with the characteristics of the vulcanizates of the prototype. The composition of the initial mixture, May. hours without modifiers: SKN-40100 Soot TM-15120 Zinc oxide5 Stearic acid1 Altax2 Sulfur2 The prototype mixture contains an additional 30 May. including methacrylic esters of unsaturation 3.5 wt.h. alcohols of the Cj-C 2 fraction of non-saturated hydrocarbon. As can be seen from the table. 3 mixtures modified by OBDL-MA, superior to the mixture according to the prototype, in terms of strength, relative elongation, at 10–40 May. h. OBD-MA - in terms of resistance to multiple stretching, the remaining characteristics remain approximately at the same level. In tab. Table 4 shows a comparison of the main characteristics of vulcanizates based on SKN-26, modified 1n 1x OBDL-MA, with the characteristics of vulcanizates of 1 modified with oligocarbonate methacrylate (OCM). The composition of the initial mixture, May. hours, without modifiers: SKN-26100 Soot DG-10045 Zinc oxide5 Stearic acid1.5 Peroximone1.25 Mixture 1 contains 10 wt.%. (example 3) and 30 wt.h. (Example 4) oligocarbonate acrylate. From tab. 4 shows the advantages of the OBDL-MA modifiers for resistance to heat aging and especially for their dynamic characteristics. Comparison of the characteristics of vulcanizates based on SKS-30 ARKM-15, modified by OBDL-MA, with the characteristics of vulcanizate, modified with CMM 1 (example 7) The composition of the initial mixture, May. h .: SKS-30 ARKM-15100 Soot DG-100. , 40 Zinc oxide 5 Stearic acid 1.5 Peroximon2 Modifier 10 From the table. 5 shows the advantage of administering BDL-MA. Improved: relative elongation, elasticity, and heat stabilities while maintaining the other characteristics. Thus, the proposed oligodiandiacrylates can significantly improve a whole range of indicators of black and non-polypropylene vulcanizates based on various synthetic rubbers without sacrificing other characteristics, although in different mixtures a positive effect is achieved for various indicators. Table 1

Resistance to rupture, MPa

16.5

Relative

elongation,%

460

Residual

elongation,%

Hardness

65 TM, usl. units

The coefficient of thermal aging at 130 ° C in air for 48 hours

relative elongation

85

11.5

15.0

11.0

410

450

460

7175

65

64

0.8

0.3

0.4

0.8

0.35 0.9

9095

75

thirty

Strength, MPa

27

Relative

elongation at

.750

gap,%

Residual

ten

5%,%

TM-238 hardness

Thermal aging coefficient

YuOSh72 h on air strength

relative elongation

Resistance

multiple

stretching

(SMR), thousand cycles Modifier OBDL-MA Properties

Strength, MPa

14

Relative lengthening, /

Residual

10 elongation,%

Hardness by. 66

table 2

26

24

32

800

780

750

14

sixteen

eight

36

35

42

0.87

0.89

0.85

0.80

0.90 0.95

700

800

820

Table 3

15

11.5

18

480

480480

450

65

66

6865 (ivrac.4.) Prototype Blend Example S

The coefficient of thermal aging X 72 hours at the point of strength

relative elongation

105

Strength, MPa

22

26

Elongation at break,% 440

450

Residual elongation,%

12

278

75 0.75

0.78

OU

0.70 0.75

120 103

1065426

ten

Continued table. 3

0.80

0.80

0.81

0.95

0.90 0.88

130115

BY

105

Table 4

31

25

27

28

450450

450

460

sixteen

12

sixteen

73

73

78

75

0.8

0,600,70

0.40

0.9

0,700,60

0.35

45

BY

and

Strength, MPa

Otnoostelny uksshshenie at raivan,%

Residual elongation

Rebound elasticity,%

Coefficient of thermal aging x 48 h Tso elasticity

1065426

12 Table 5

thirty

thirty

680

750

14

ten

40

60

0.60

0.85

Claims (1)

METHOD FOR PRODUCING OLIGOMERS WITH END ACRYLATE GROUPS by reacting a hydrocarbon with functional end groups with an addition agent in an organic solvent medium, characterized in that, in order to improve the physicomechanical properties of vulcanizates containing the target product, diLithioligo * is used as a hydrocarbon with functional end groups Diene of the general formula IN Z1T sn-sn _d zi, where R is H, CHj; η = 21-187, and the interaction process is carried out by treating dilithioligodiene with 1.0-3.3 mol of ethylene oxide per 1 mol of active lithium, followed by the introduction of acrylic acid chloride into the reaction mixture or methacrylic acid, and the process is carried out at a molar ratio of ethylene oxide and acid chloride of acrylic or methacrylic acid (1: 1) to (3.3: 1), respectively. SU „1065426