SU1437371A1 - Polyisocyanurate as linking agent of mouldable polyurethanes and method of producing same - Google Patents

Abstract

This invention relates to the field of synthesis of polyisocyanurates (PNC) with terminal isocyanate groups and can be used as a crosslinking agent for urethane elastomers (CI). The invention allows to simplify the process of crosslinking the UE due to the solubility of PICs having the following structure: 1 (L

Description

where R is the residue of the diol mol, m, 104-500, selected from the group comprising H-methyl-1,3-butanediol, Hexanediol, triethylene glycol, oligoethylene di-ethylene glycol adipate (DO). Mol.m. PIC 1180-1580, the content of NCO-rpynn is 32.5-34.2%. PICs are prepared by the interaction of 2,4-toluene diisocyanate (TDI) with DO in a molar ratio of 2: 1 per

for 5-8 min, followed by heating to 8015 s and cooling to with stirring. The resulting product is additionally injected with 4 mol of TDI and 0.15 by weight of TDI of 2-methylaminomethylphenol is heated to C and benzoyl chloride is introduced. Next, the PIC is cooled and abraded. 2 tab.

four; with so

--four

Ignes ns- polikzotsk-

g (2 mol.) (TDI) with

The invention relates to 1: 2 polyisocyanates, in particular, is obtained. Neither triisocyanurates with free isocyanate groups, and can be used as crosslinking agents in the synthesis of molded urethane elastomers.

The purpose of the invention is the synthesis of polyisocyanurate 5 capable of dissolving: - c in polyester, which makes it possible to use it: to shed it as a cross-link

agent when receiving and polkuretan "

injection type

The goal is to achieve the chemical structure of anurat

With an agitation (1 mol) of 3-methyl 1; 3-butanediol of molecular weight 104 is added with stirring to 30.3 2, 4-toluenediisomes.anate and with stirring for 5 microns, the resulting product. is a transparent sight. The reaction mass is cooled down to 40 ° C and the prod: g; r is mixed: g (4 mol) TDI to 2-cymethylaminomethylphenol in the amount of Oz15% of the EUI TDI. Raise the temperature of the reaction mass to 120 ° C; 5 ° C at the transition; - by stirring, banzoic chloride is introduced; in quantity, the equivalent of - ;; ohm amount of catalyst 5 and cool “The resulting monolithic mass of powder and powder. The yield of 93%.

For identification, the product is pacTj; io is ry in th oroform and salted out with diethyl ether by means of a lime method. After filtering and drying, they are identified by means of IR spectroscopy. In the IR spectrum, intense lolos are observed; absorption 1420, 1.710 ,, responsible for the triiso group: the ianuritical cycle, absorption band 1190 cm, responsible for the urethane group (-NHCOO-), absorption band 2275 ZM responsible for NCO-rpy. iny isotsack - anurate, Molecular mass is equal

Calculated 1148

Found 1180

Content of free LSS groups,%

Calculated33, jJ

Found34, 1

A quantitative and qualitative analysis of the elementary analysis was carried out (calculated for C; gIi j; VP-i4)

Calculated 5 / N 4,18

C 61., 6; ;

14,

Found,%: C 61 .5G., N 14.74; H 4s25.

Based on the conducted studies, J. the structure of the compound corresponds to the structure of the polyisocyanurate according to claim 1

EXAMPLE 2. To 29.94 g (2 mol) of TDI, with stirring, 1Q 10 15 15 (1 mol) of hexanediol, 118 molecular weight, is poured at 5-6 min 5 is cooled to 40 ° C and poured at stirring 59, (4, mol) TDI and 2-dimethyl shnometil-15 phenol in an amount of 0.15% by weight of TD1-1. The temperature is raised to 1201 i 5 C and chlorine benzoyl is added with stirring in the proportional ratio to the catalyst (1: 1) and cooled is given

The resulting mass is ground into powder g,

Identified; is carried out as in Example 1; 25 the same spectra are observed in the IR spectra as in Example 1.

Molecular weight;

Calculated 1162

Found1201

Content of free NCO rpynn5%: 30 Calculated 33

Found

Analysis calculated for C oHjo -iiOw

Calculated,%: C N 14.45,

H 4;

%%: C, 61.84; N v 4, .45.

The structure of the compound corresponds to the structure of the polyisocyanurate according to claim 1, of the formula.

The content of NCO-rpynn was determined by a known method.

The molecular weight is determined by an ebulioscopic method.

Example 3 The method is carried out as in Example 1. As the diol, triethylene glycol (TEG) of molecular weight 150 is used. To 29.14 g (2 mol) of TDI, 12.56 (1 mol) of TEG are poured and 58.29 g (4 mol) of TDI was added to the resulting product. The resulting mass is ground into powder. Identification is carried out as in Example 1. The same absorption bands are observed in the IR spectra as in Example 1. Molecular weight: Calculated: 1194

Found 1220

Content NCO-rpynn,%:

Calculated33

35

40

45

Found34

L and l and 3 p and with with and h about. D l Cjjj, 0, nd.

Calculated ,,%: C 60.30; N 14.08; K 4, 1 8.

Found,% C 60,12; N 13.88; H 4.21.

The structure of the compound corresponds to the structure of the polyisocyanurate according to claim 1 of the formula, 10

Example 4: The method is carried out as in Example 1, but oligohexydiethylene glycol-lipadipate of molecular weight 300 (OEDA) is used as the diol., 5

i (25.89 g (2 mol) TDI, 22.32 (1 mol) OEDA is poured and L1., 78 g (4 mol) TDI., the resulting crystalline mass is powdered, 20

In the IR spectra 1; there are ab; those; xe bands as in example 1.

Molecular weight:

Calculated1344

Found 137025

Contents YSO-group; %five

Calculated33

Naaydi.O33,8

Analysis calculated for Cgj ,,, pa, 7 30

Calculated: 7, i С 55.24 N 11.37; 4.74

Found,%; C 55.48 N 4.52

The structure of the compound corresponds to the structure of the polyisocyanurate at u, i. . emuls

EXAMPLE 5. The method is carried out in example 15 HC. OEDA is used as the diol of molecular weight 433.

29.31 g (1 mol) OEDA is added to 23556 g (2 mol) of the TDI and 47.12 g (4 mol) of the TDI is added to the resulting product. The resulting mass is ground into powder,. , four

In the IR spectra, absorption bands are observed as in Example 1,

Molecular weight:

Calculated1477gg

Naida: u1505

Content of NCO-groups,%;

Vigchi „Leno33

Found 33; 8

Analysis (calculated; for CgjIi jN.j}) 55

Calculated,%: C 55; 24; N 11.37; S 4.74.

Found %: C 55.48; N 11.15; H 4.52.

35

The structure of the compound corresponds to the structure of the polyisocyanurate according to claim 1 of the formula.

EXAMPLE 6: The method is carried out 1; aql ave; -; least 1 ,, but as the diol, an OEG of molecular weight 500 is used,

32.38 (1 mol) OEDA was poured to 22.55 (2 stranded) TDIs and 45.07 g (4 stranded) TDI was added to the resulting product. Mass: 1 powdered.

-: Olekul rna ma ssa:

calculated1544

1580

The content of CSR groups

0

five

0

g

five

five

15th anniversary

33 32.7

Analysis (calculated for CyaHjjNiiOj) t

Calculated,%: C 50, N Sh. 88; H 5.31

Found S%: C 60.41, N 10.69; li 5.53.

The structure of the compound corresponds to the structure of a polyisocyanurate according to claim 1 of the formula

Example 7 Hcontrolled), To 30.68 g (2 mol) of TDI, 7.9 g (1 mol) of 1,4-butadiol of molecular weight 90 are added with stirring at and stirred for 5 minutes, then 61.37 g are poured (4 mol) TDI, but dissolution does not occur. To obtain a compound with a structure corresponding to the structure of the polyisocyanurate according to claim 1, the formula is not possible,

EXAMPLE 8 (control), K 21.83 g (2 mol) of TDI with a stirrer add 34 ,, 50 g (1 mol) of OEG of molecular weight 550 at BOt i 5 s and stirring T for 5-6 min. Then it is cooled to 40 ° C and 43.66 g (4 mol) of TDI and 2-dimethylaminomethylphenol in the amount of 0.15% by weight of semi-compound are added with stirring. Raise the temperature before and with stirring; lorinous benzoyl in an amount equimolecular with the amount of catalyst (1: 1). Then cooled,

The resulting product is insoluble in solvents and polyester.

Example 9 (control)., The synthesis is carried out as in example 1, but the reaction temperature is 1 mol of 3-methyl-153-butanediol and 2 moles of TDI reduced to 74 ° C. At this temperature, there is no complete interaction and nojui ™

cooling

up to 50 s and surging

the isocyanurate of claim 1 is not formed.

Example 10 (control B5). The synthesis is carried out as in example 1, but at 87 s, the compounds with the structure according to A.1. Formulas are obtained, but with greater energy consumption.

Example 11 (control), C, is carried out as in Example 1, but for 4 minutes. Full interaction does not occur. The compound is insoluble in polyesters.

 PRI me R 12 (control). The synthesis is carried out as in 1, but the reaction mass lead

k mole TDI to catalyst.

The product is soluble in polyester.

Example 13 (control). The test is carried out as in Example 1, but the reaction temperature of the PODNEMNEOT reaction is before the inhibitor is introduced and cooled.

Get in a viscous liquid. During the synthesis of molded polyurethane in the presence of its curing does not occur

Example 14 (control) Synthesis is omitted as in Example 1, but the temperature is raised to 130 ° C.

Due to the high viscosity, it is not possible to introduce an inhibitor. The viability of polyisocyanurate is negligible.

Example 15 (control). Synthesis is carried out as in Example 1, but catalysts take 0.14% by weight of TDI,

The process is not completely, and det.

Example 16 (control). The synthesis is carried out as in Example 1, but the catalyst is 6epyt by weight of TDI. The reaction becomes uncontrollable; - mine.

The polyisocyanurates prepared according to examples 1-6 were tested as a crosslinking agent in the synthesis of injection-type polyurethanes.

Example 17. (control by a known method). 51.42 grams of a 40% solution of triiso- ananate in butyl acetate are poured into 79.41 g of pre-dried PE A of the 2014 mass (since triisocyanurate dissolves 5 in the starting polyether). c butyl acetate). The ratio of NCO-rpynn to OH groups is 1: 1.

Synthesis of vudet at 120 ° C and a residual pressure of 667 Pa to complete the removal of the solvent for 30 hours,

Because of this, the npti 12Q C is carried out in 20–25 h.

Samples ByaerZh1-: wallow on Tet Tet; eKHe 14 s u t and s p y ti m. Sung urethanes Greds

PRI m e): PREDIDA j i k j Kyy: HpKoft: - i, it; Cb omeshivaniya; 23

, (, erzh 3, flakvl; b 7 6jb 1,

18. 3 77.82 Y (1 -; ol Bbicyuiejuicro GgEA g-melanohydrate at pe- 7 g (OJ5 mol) connect 5

Q

0

0

five

0

Nominal pressure of enamel L67 for up to jicji Htjro dissolution;: orO1ik s te-1e not 30-40 min. After this river: a mass is poured by gravity i p; el8Bb; e form No. 1. Curing is carried out; 1 120 C for 20-25 hours,

Failure ::; resistance of polyurethane to heat loss is carried out with a dog; from theokocamera with their subsequent rupture, GO GOST GOST 270-75 (table. O,

P p and g;:;; 19 about Ci-iHT they knew GI: -but g; rikeru ve crosslinking agent and the compound according to example 2.,

SoprotiL; niya gap rupture-. In elastokeres during the process of thermal aging, they are listed in Table 2.

Example 201 Synthesis of the 5th-but-11th Synthesis; are using

are as in the example of an agent in leu with measure 3 „

Note D 2 i

- / intez

carried out anahyugi-example 15, As a crosslinking agent, the compound of example 4,

APPENDIXES: e 22, Synthesis is carried out analogously, as in examples 15, and the compound used in the quality of the cross-linking agent is 3: 5.

Example 23, the synthesis is carried out analogously to example 15., As a cross-linking agent, the compounds obtained by G o make-up artist 6, Forms at Ji a and 3 about 5 retem y, are used.

 , zooianurat of the general formula:

uh

n, s-oh oh

About with:

n,

CSR

:; about

-Shz

nso

TSICO

NZS

Shz

NCO

HNCOOROOC-NH

where R is the residue of the diol mol, m, 104500, selected from the group,

including; 3-methyl-1,3-butanediol, hexanediol, triethylene glycol, oligoethylene ethylene glycol adipate mol.m. 1180- 1580 and an isocyanate group content of 32.5-34.2%, which is characterized by the fact that 2,4-toluene diisocyanate interacts with the compound in the polyether solubility in polyether; -500 selected from the group comprising 3-methyl1, 3-butanediol, hexanediol, triethylene glycol, oligoethylene-ethylene glycol adipate, in a molar ratio of 2: 1 and for 5-8 min, followed by heating with stirring before cooling to introduction with stirring of 4 mol of 2,4-toluene diisocyanate and 0.15% by weight of 2,4-toluene diisocyanate 2-di-mime tylaminomethylphenol and heating to 12015 ° C and introducing benzoyl chloride in an amount equimolecular to the amount of 2-dimethylaminomethylphenol, cooling and abrasion.

Table 1

Claims (2)

1.3- butanediol, hexanediol, triethylene glycol · 2Q, oligoetilendietilenglikol- adipate, in a molar ratio of 2: 1 and for 5-8 minutes, followed by heating with stirring to about 80 * C 5 ^minutes and cooled to 35-5 ° C, vve25 deniem with stirring 4 mol 1. Polynzocyanurate of the General formula: “With ... 'Jk ^OT · ΰ- · - · 3 ^Ζ . .С = 0 I ^U ”J O si, ЖО NC0 where R is the remainder of the diol, mol. 104–500, selected from the group consisting of 3-methyl-1,3-butanediol, hexanediol, triethylene glycol, oligoethylene diethylene glycol — adipin. 1180-1580 and the content of NCO groups equal to 32.5-34.2%, as a crosslinking agent in the production of injection-type polyurethanes. 2. The method of obtaining polyisocyanurates of the General formula N00 NCO ^NZS ~ O_ | ? _G ^ch '° = ^С \ / Ν- / Λ-ΗΝ000Η000 · ΝΗηΟν < ^{0 N} ^ C = 0 N — with H ⁷ 4 = ⁷ s — N ^CHs about ^DOS , N00 where R is the remainder of the diol mol. m. 11801580 and the content of isocyanate groups equal to 32.5-34.2%, characterized in that, in order to give the polyisocyanurate solubility in polyester, 2,4-toluene diisocyanate interacts with the compound mol.m. 104-500 selected from the group comprising 3-methyl- 2.4- toluylene diisocyanate and 0.15% by weight of 2,4-toluene diisocyanate of 2-dimethylaminomethylphenol and heated to 120i5 ° C and the introduction of benzoyl chloride in an amount equimolecular to the amount of 2-dimethylaminomethylphenol, cooling and abrasion.