WO2007116761A1

WO2007116761A1 - Diphenylmethane isocyanate composition

Info

Publication number: WO2007116761A1
Application number: PCT/JP2007/056466
Authority: WO
Inventors: Takeo Takeda; Tatsuya Yamaguchi; Tomomitsu Yoshihara; Susumu Yamada; Yoshiyuki Kanbara
Original assignee: Nippon Polyurethane Industry Co., Ltd.
Priority date: 2006-03-30
Filing date: 2007-03-27
Publication date: 2007-10-18
Also published as: CN101415671A; JPWO2007116761A1

Abstract

Disclosed is a diphenylmethane isocyanate composition comprising a composition which is obtained by adding an alkylchlorosilane having 4-24 carbon atoms in total in the molecular structure to a diphenylmethane isocyanate having an acid degree of less than 0.1% by mass. This diphenylmethane isocyanate composition has a high acid degree of not less than 0.1% by mass. The alkylchlorosilane is preferably 1,3-dichlorotetraisopropyldisiloxane or triethylchlorosilane. The diphenylmethane isocyanate composition takes a longer time before starting to increase in viscosity (namely, has a higher storage stability) than the conventional ones.

Description

Specification

Diphenylmethane isocyanate composition

Technical field

[0001] The present invention relates to a diphenylmethane-based isocyanate composition that can be used in the production of various polyurethane products.

Background art

[0002] For the production of various polyurethane products, diphenylmethane isocyanate compositions having a predetermined acidity may be used. The diphenylmethane-based isocyanate composition having the predetermined acidity is preferable as a raw material for, for example, rigid polyurethane foam.

[0003] The "acidity" here means a value obtained by converting an acid component that reacts with alcohol at room temperature and liberated into hydrogen chloride, and is measured in accordance with JIS K-1603 (1985). . The same applies hereinafter.

[0004] The diphenylmethane-based isocyanate composition as described above is also disclosed in Patent Document 1 below.

[0005] Patent Document 1: Japanese Patent Laid-Open No. 2005-220137

Disclosure of the invention

Problems to be solved by the invention

[0006] However, the diphenylmethane isocyanate composition disclosed in Patent Document 1 can reduce the variation in acidity by intentionally setting the acidity to a predetermined value, but it can be stored over time. It seems that the stability, especially the storage stability at high temperature such as 45 ° C-constant atmosphere, deteriorates (viscosity increases (thickening)) and tends to increase.

[0007] Such a thickening of dimethane methane isocyanate causes problems in the production of polyurethane resin. For example, when the user and the manufacturer are at a long distance, the diphenylmethane isocyanate composition thickens due to the passage of a certain period during transportation, or the period when the diphenylmethane isocyanate yarn and the composition start to be used suddenly. Is extended When this thickened diphenylmethane isocyanate composition is used for the production of polyurethane resin, the mixing with polyols becomes non-uniform and the reactivity is increased. It may not be possible to produce a desired polyurethane product, such as non-uniformity (variability in reactivity).

[0008] Accordingly, an object of the present invention is to provide a diphenylmethane isocyanate composition having a longer period of time for thickening than the conventional one (high storage stability).

Means for solving the problem

[0009] The present invention includes a composition obtained by adding an alkylchlorosilane having a total carbon number of ˜24 in a molecular structure to a diphenylmethane isocyanate having an acidity of less than 0.1% by mass. It is a diphenylmethane isocyanate composition having a high acidity and an acidity of at least mass%. The alkylchlorosilane is preferably 1,3-dichlorotetraisopropyldisiloxane or triethylchlorosilane. The invention's effect

[0010] According to the above configuration, it is possible to provide a diphenylmethane isocyanate composition that has a longer period of time for thickening than the conventional one (high storage stability).

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] The diphenylmethane isocyanate composition according to the embodiment of the present invention will be described below.

[0012] The diphenylmethane isocyanate composition according to the present embodiment is obtained by adding an alkylchlorosilane having a total carbon number power of -24 in a molecular structure to a diphenylmethane isocyanate having an acidity of less than 0.1% by mass. And a high acidity composition having an acidity of 0.1% by mass or more.

[0013] Diphenylmethane isocyanate is a mixture of dinuclear MDI (diphenylmethane isocyanate) and trinuclear or higher polynuclear (MDI condensate) (polyphenylene polymethylene polyisocyanate). It is. This diphenylmethane isocyanate can be obtained by converting the amino group of a condensation mixture (polyamine) obtained by the condensation reaction of aline and formalin to an isocyanate group by phosgene or the like. By changing the composition ratio of the raw materials and the reaction conditions during condensation, the final diphenol The composition of tan-based isocyanate (nuclear distribution and isomer composition ratio) can be controlled.

[0014] In addition, diphenylmethane-based isocyanate is used for reaction conditions and separation conditions such as the reaction liquid after conversion to isocyanate group, the reaction liquid power is also removed from the solvent, and the bottom is partially distilled off from MDI. It may be a mixture of several different types. Further, commercially available diphenylmethane isocyanate may be mixed with MDI.

[0015] The proportion of MDI in the dimethane methane isocyanate is preferably 20 to 80%, more preferably 40 to 60%. The ratio of MDI here is the ratio for which the peak area specific power of MDI by GPC (gel permeation chromatography) is also obtained.

[0016] MDI, which is a binuclear body, is composed of three isomers: 4, 4'- MDI, 2, 2'- MDI, and 2, 4'- MDI. The composition ratio of isomers can be determined from a calibration curve based on the area percentage of each peak obtained by GC (gas chromatography).

[0017] The average number of functional groups of the diphenylmethane isocyanate is preferably 2.2 or more, more preferably 2.2 to 3.1. Further, the isocyanate group content of diphenylmethane-based isocyanate is preferably 28 to 33% by mass, more preferably 28.5 to 32.5% by mass.

The acidity of the diphenylmethane isocyanate having an acidity of less than 0.1% by mass used in the present invention is preferably a diphenylmethane isocyanate (low acidity product) that is generally at the above-mentioned acidity level. In view of the above, it is preferably 0.05% by mass or less, more preferably 0.03% by mass or less.

[0019] The total number of carbon atoms in the alkyl chlorosilane having a total carbon number in the molecular structure to 24 is the total number of carbon atoms of the alkyl group or the alkyl group and alkylene group bonded to the silicon atom which may be plural. For example, the total number of carbons in triethylchlorosilane is 6, and the total number of carbons in 1,3-dichlorotetraisopropyldisiloxane is 12.

[0020] Examples of alkyl chlorosilanes having a total carbon number power of -24 in the molecular structure are listed below.

(1) A compound in which three chlorine atoms and one saturated hydrocarbon group are bonded to one silicon atom in the molecular structure, such as n-butyltrichlorosilane, isobutyltrichlorosilane, pentyl Rutrichlorosilane, hexyltrichlorosilane, cyclohexyltrichlorosilane, heptyltrichlorosilane, octyltrichlorosilane, nonyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, tetradecyltrichlorosilane, octadecyltrichlorosilane, eico Siltrichlorosilane, etc.

(2) Compounds in which two chlorines and two saturated hydrocarbon groups are bonded to one silicon in the molecular structure, for example, jetyldichlorosilane, methylpropyldichlorosilane, butylmethyldichlorosilane, methylpentyl Dichlorosilane, cyclohexylmethyldichlorosilane, hexylmethyldichlorosilane, heptylmethyldichlorosilane, dibutyldichlorosilane, methyloctyldichlorosilane, decylmethyldichlorosilane, dihexyldichlorosilane, dodecylmethyldichlorosilane, methyloctadecyl Dichlorosilane, etc.

(3) A compound in which one chlorine and three saturated hydrocarbon groups are bonded to one silicon in the molecular structure, for example, triethylchlorosilane, tripropylchlorosilane, tributylchlorosilane, trihexylchlorosilane, Dimethylpropylchlorosilane, dimethylisopropylchlorosilane, tert-butyldimethylchlorosilane, dimethyloctylchlorosilane, dimethyloctadecylchlorosilane, etc.

(4) A compound in which one chlorine and two saturated hydrocarbon groups are bonded to each of two silicons having siloxane bonds in the molecular structure, for example, 1, 1, 3, 3-tetramethyl-1, 3-dichlorodichlorosiloxane, 1,3-dichlorotetraisopropyldisiloxane, etc.

(5) A compound in which two chlorine atoms and one saturated hydrocarbon group are bonded to each of two silicon atoms alkylene-bonded in the molecular structure, for example, 1,2-bis (methyldichlorosilyl) ethane etc,

(6) A compound in which one chlorine and two saturated hydrocarbon groups are bonded to each of two silicon atoms alkylene-bonded in the molecular structure, for example, 1,2-bis (dimethylchlorosilyl) ethane Etc. When adding to diphenylmethane isocyanate, a mixture of two or more of the above examples of alkylchlorosilane may be used.

According to the above configuration, it is possible to provide a diphenylmethane isocyanate composition that has a longer period of time for thickening than the conventional one (high storage stability).

Example [0022] In all the examples and all the comparative examples, the diphenylmethane isocyanate shown below having a low acidity was prepared as the diphenylmethane isocyanate used.

Acidity = 0.011 mass%

MDI (binuclear) peak area ratio = 40%

* MDI peak area ratio was also calculated by GPC force.

4, 4 'MDI content in MDI (binuclear body) = 99%

* 4, 4 '— MDI content in MDI was also calculated by GC power.

Isocyanate group content = 31.0% by mass

[0023] The isocyanate group content (hereinafter abbreviated as “NCO content” in the following tables and all comparative examples, and “NCO% (mass%)” in the table below) is as follows. It measured by the measuring method shown.

(1) About 0.5 to 1. Og of the sample whose NCO content is to be measured is precisely weighed into an Erlenmeyer flask (internal volume 300 ml).

(2) Add 20 ml of a 0.5 molZl dibutylamine monochlorobenzene solution to the above Erlenmeyer flask, and gently leave it for 15 minutes after stirring.

(3) Add 100 ml of methanol and 1 drop of bromophenol 'blue indicator to the above Erlenmeyer flask, and perform back titration on the contents of the flask using 0.5 molZl hydrochloric acid standard solution. At this time, the titer of the hydrochloric acid standard solution required for the titration of the sample is A (ml).

(4) The same operation as in the above (1) to (3) is performed to obtain a “blank” sample. The blank is titrated in the same manner as (3) above. At this time, the titration volume of the hydrochloric acid standard solution required for the blank titration is B (ml).

(5) The end point of the titration is the point at which the blue color of promofenol blue indicator turns yellow

(6) Calculate the NCO content using the following formula.

NCO content (mass ⁰ /.) = [(BA) X 42 X 0.5 X f] X 100 ÷ (SX 1000) In the above formula,

A: Titration of 0.5 molZl hydrochloric acid standard solution required for titration of sample (ml)

B: Titration of 0.5molZl hydrochloric acid standard solution required for blank titration (ml) f: Factor of 0.5 molZl hydrochloric acid standard solution

S: Sampling amount (g)

Respectively.

[0024] Viscosities in all Examples and all Comparative Examples were measured by a method according to JIS K2283 (1980) using a Cannon Fenceke viscometer. The outline of the measurement method is as follows.

(1) Place a sample whose viscosity is to be adjusted to 25 ° C in a Canon Fenceke viscometer and place it vertically in a constant temperature bath adjusted to 25 ° C for a predetermined time.

(2) After the sample in the viscometer reaches the specified temperature, measure the outflow time t (s) by the method shown in JIS K2283 (1980).

(3) Calculate the kinematic viscosity by the following formula.

V = C X t

In the above formula,

V: Kinematic viscosity (cSt) {mm ² Zs}

C: Viscometer constant (cStZs) {mmVs ² }

t: Outflow time (s)

Respectively.

(4) The static viscosity (mPa's) is calculated by multiplying the kinematic viscosity obtained by the above equation by the specific gravity of the sample.

[Example 1]

Said Jifue acidity 0. 011 mass ^_0/0 - relative Rumetan system Isoshianeto 500 g, 1, 3-dichloro-tetraisopropyl disiloxane 4. added 4g, was adjusted acidity to 0.216 mass% Jifue A dimethane-based isocyanate composition was prepared, and the NCO content after the preparation and the rate of change in viscosity over time (from 0 to 6 weeks per week) were measured at 45 ° C in a constant atmosphere. The results are shown in Table 1 below. In addition, the acidity in the table is an actual measurement value of the produced diphenol methane isocyanate composition (the same applies hereinafter) o

[0026] [Table 1] Acidity (%) NC0 (%) Change rate Viscosity (mPas) Change rate

0 weeks 30. 8 0% 198 0%

1 week 30. 7 0% 198 0%

2 weeks 30. 7 0% 201 2%

3 weeks 0. 216 30. 7 0% 203 3%

4 weeks 30. 7 0% 205 4%

5 weeks 30. 7 0% 207 5%

6 weeks 30. 6 0% 208 5%

[Example 2]

Against diphenylmethane series Isoshianeto 500g acidity 0. 011 wt% said, tri E chill chlorosilane 4. 2g添Ka卩, Jifue was adjusted acidity to 0.213 mass ^_0/0 - Methane system Isoshianeto composition The NCO content and viscosity change over time (0 weeks to 6 weeks for each week) were measured at 45 ° C in a constant atmosphere. The results are shown in Table 2 below.

[0028] [Table 2]

[0029] (Comparative Example 1)

NCO content of the above diphenylmethane isocyanate having an acidity of 0.011% by mass In addition, the rate of change with time in viscosity (from 0 to 6 weeks every week) was measured at 45 ° C in a constant atmosphere. The results are shown in Table 3 below.

[0030] [Table 3]

[0031] From Tables 1 to 3, in the diphenylmethane isocyanate compositions of Examples 1 and 2, the viscosity changes over time with respect to that of Comparative Example 1 which is a low acidity product despite being a high acidity product. It can be seen that the rate is the same or low.

[0032] (Comparative Example 2)

It said Jifue acidity 0. 011 mass ^_0/0 - Rumetan system Isoshianeto 500 g, was charged to the 1L flask equipped with a blowing tube and a stirrer were connected float type flow meter, through the blowing tube at a controlled flow rate Dichloromethane-based isocyanate composition with hydrogen chloride gas blown and acidity adjusted to 0.200% by mass was prepared, and NCO content and viscosity change rate over time after preparation (0 to 6 weeks every week) Was measured at 45 ° C in a constant atmosphere. The measurement was discontinued after 3 weeks due to the significant change over time (thickening). The results are shown in Table 4 below.

[0033] [Table 4] Acidity (%) NCO (%) Change rate Viscosity (mPa's) Change rate

0 weeks 30.9 0% 182 0%

1 week 30.5 -1% 297 63%

2 weeks 30.5 -1% 332 82%

3 weeks 0.200 30.3 -2% 358 97%

4 weeks | B, 1 1 1 1

5 weeks 1 1 1 1

6 weeks 1 1 1 1

[0034] From Tables 1, 2 and 4, the diphenylmethane isocyanate composition of Examples 1 and 2 is! /, Which is simply the high acidity of Comparative Example 2, and the rate of change with time in viscosity. It is clear from the results after one week that it is clearly superior.

[0035] (Comparative Example 3)

To 500 g of the above diphenylmethane isocyanate having an acidity of 0.011% by mass, 2.15 g of 3,3,3-trifluoropropyltrichlorosilane was added to adjust the acidity to 0.222% by mass. A diphenylmethane isocyanate composition was prepared, and the NCO content after the preparation and the rate of change in viscosity over time (from 0 to 6 weeks every week) were measured at 45 ° C in a constant atmosphere. The results are shown in Table 5 below.

[0036] [Table 5] Acidity 0 NCO (%) Change rate Viscosity (mPa's) Change rate

0 weeks 30.9 0% 201 0%

1 week 30.9 0% 208 3%

2 weeks 30.9 0% 215 7%

3 weeks 0.222 30.8 0% 229 14%

4 weeks 30.7 -1% 271 35%

5 weeks 30.7 -1% 274 36%

6 weeks 30.6 -1% 279 39% [0037] (Comparative Example 4)

Said Jifue acidity 0. 011% by weight - relative to Rumetan system Isoshianeto 500 g, Hue - Le trichlorosilane with 1. 95 g添Ka卩, Jifue was adjusted acidity to 0.220 mass ^_0/0 - Rumetan system An isocyanate composition was prepared, and the NCO content and viscosity change over time after preparation (0 to 6 weeks per week) were measured at 45 ° C in a constant atmosphere. The results are shown in Table 6 below.

[0038] [Table 6]

[0039] (Comparative Example 5)

Said Jifue acidity 0. 011 mass ^_0/0 - relative Rumetan system Isoshianeto 500 g, Jifue Nirumetan of diphenyl dichlorosilane and 3. 65 g添Ka卩was adjusted acidity to 0.215 mass ^_0/0 A system isocyanate composition was prepared, and the NCO content and viscosity change rate after preparation (0 to 6 weeks for each week) were measured at 45 ° C. in a constant atmosphere. The results are shown in Table 7 below.

[0040] [Table 7] Acidity (%) NCO (%) Change rate Viscosity (mPa's) Change rate

0 weeks 30.8 0% 201 0%

1 week 30.8 0% 208 3%

2 weeks 30.8 0% 212 5%

3 weeks 0.215 30.8 0% 214 6%

4 weeks 30.7 0% 230 14%

5 weeks 30.7 -1% 243 21%

6 weeks 30.5 -1% 260 29%

[0041] (Comparative Example 6)

2. Dichloromethane isocyanate composition prepared by adding 2.85 g of isophthalic acid dichloride to 500 g of the above diphenylmethane isocyanate having an acidity of 0.011% by mass and adjusting the acidity to 0.249% by mass. Then, the NCO content after the preparation and the rate of change with time of the viscosity (from 0 weeks to 6 weeks every week) were measured at 45 ° C in a constant atmosphere. The results are shown in Table 8 below.

[0042] [Table 8]

[0043] (Comparative Example 7)

Based on 500 g of the diphenol methane isocyanate having an acidity of 0.011% by mass 2.85 g of (ortho) phthalic acid dichloride was added to the diphenylmethane isocyanate to prepare a diphenylmethane isocyanate yarn with an acidity adjusted to 0.197% by mass, and the NCO content and viscosity after the preparation. Was measured at 45 ° C in a constant atmosphere (0 to 6 weeks every week). The results are shown in Table 9 below.

[0044] [Table 9]

[0045] (Comparative Example 8)

Against acidity 0.011 wt% a is said Jifueerumetan system Isoshianeto 500 g, terephthalic acid dichloride 2. 85g添Ka卩, Jifue was adjusted acidity to 0.210 mass ^_0/0 - Rumetan based Isoshianeto composition After the preparation, the NCO content and the rate of change with time of the viscosity (from 0 to 6 weeks per week) were measured at 45 ° C in a constant atmosphere. The results are shown in Table 10 below.

[0046] [Table 10]

Acidity (%) NCO (%) Change rate Viscosity (mPa-s) Change rate

0 weeks 31.0 0% 201 0%

1 week 31.0 0% 229 14%

2 weeks 30.9 0% 261 30%

3 weeks 0.210 30.8 -1% 286 42%

4 weeks 30.7 -1% 323 61%

5 weeks 30.6 -1% 356 77%

6 weeks 30.5 -2% 398 98%

[0047] Tables 1, 2 and 5 ~: From LO, the rate of change with time of viscosity can be suppressed for up to about 4 weeks even in Comparative Examples 3-8 (see Comparative Example 5). It can be seen that the diphenylmethane isocyanate composition can suppress the rate of change with time of viscosity for a longer period (up to about 6 weeks).

[0048] (Example 3)

To 500 g of the diphenylmethane isocyanate having an acidity of 0.011% by mass, 2.5 g of 1,3-dichlorotetraisopropyldisiloxane was added to adjust the acidity to 0.129% by mass. A series of isocyanate composition is prepared, and the time-dependent change rate of viscosity after preparation (0 曰, 7 曰, 14 曰, 21 曰, 42 曰, 80 曰) is 45 ° C—constant Measured under atmosphere. The results are shown in Table 11 below.

[0049] [Table 11]

Acidity (%) Viscosity (mPa's) Viscosity change rate (%)

0 215 0

7 days 21 7 1

14 days actual measurement; 221 3

21 days 0.129 222 3

42 days 232 8

80 days 249 16

[0050] (Example 4)

Diphenylmethane isocyanate composition in which 5.3-Og of 1,3-dichlorotetraisopropyldisiloxane is added to 500 g of the above diphenylmethane isocyanate having an acidity of 0.011% by mass to adjust the acidity to 0.252% by mass. Measure the viscosity of the film after the preparation (0 days, 7 days, 14 days, 21 days, 42 hours, 80 hours) at 45 ° C in a constant atmosphere. did. The results are shown in Table 12 below.

[0051] [Table 12]

[Example 5]

Based on 500 g of the diphenylmethane isocyanate having an acidity of 0.011% by mass 1, 3-dichloro-tetraisopropyl disiloxane 7. added 5g, to prepare a Jifue two Rumetan based Isoshianeto composition was adjusted to acidity 0.378 mass ^_0/0, over time Heni匕率of viscosity after making ( Measurements were performed at 45 ° C in a constant atmosphere at 0 to 7, 7 to 14, 14 to 21 to 42 to 80. The results are shown in Table 13 below.

[0053] [Table 13]

[Example 6]

Said Jifue acidity 0. 011 mass ^_0/0 - relative Rumetan system Isoshianeto 500 g, 1, 3-dichloro-tetraisopropyl disiloxane 10. Og added, Jifue two adjusted to acidity 0.503 wt% A methane-based isocyanate composition was prepared, and the time-dependent change rate of viscosity after preparation (0 to 7, 7 to 14, 14 to 21, 21 to 42, to 80 to 45 ° C) The measurement was performed under a constant atmosphere. The results are shown in Table 14 below.

[0055] [Table 14]

Acidity (%) Viscosity (mPa's) Viscosity change rate (%)

0 195 0

7 days 200 3

Actual measurement for 14 days; 205 5

21 days 0.503 207 6

42 days 216 1 1

80 days 226 16

[0056] (Comparative Example 9)

The viscosity change rate of the diphenylmethane isocyanate having the acidity of 0.006% by mass (0 to 7, 7 days, 14 days, 21 days, 42 days, 80 days) to 45 ° C—Measured under a constant atmosphere. The results are shown in Table 15 below.

[0057] [Table 15]

From Tables 11 to 14, the diphenol methane isocyanate compositions of Examples 3 to 6 were compared with those of Comparative Example 9 which was a low acidity product, although it was a high acidity product, after 80 days. However, it can be seen that the rate of change with time in viscosity is the same or low. . It can also be seen that even when the amount of 1,3-dichlorotetraisopropyldisiloxane added is different, the same rate of change with time in viscosity can be obtained.

The present invention can be modified within the scope without departing from the scope of the claims, and is not limited to the above-described embodiments and examples.

Claims

The scope of the claims

[1] It is characterized by containing a composition obtained by adding an alkylchlorosilane having a total carbon number of ˜24 in the molecular structure to a diphenylmethane isocyanate having an acidity of less than 0.1% by mass. A high acidity diphenylmethane-based isocyanate composition having an acidity of 1% by mass or more.

[2] The diphenylmethane isocyanate composition according to [1], wherein the alkylchlorosilane force is 1,3-dichlorotetraisopropyldisiloxane or triethylchlorosilane.