JPS59106430A - Glycol composition containing phosphorus-modified silane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to gelling-resistant aqueous glycol or glycol ether compositions containing phosphorus-modified silanes.

It is known from US Pat. No. 3,362,910. The relatively inexpensive and effective use of borax and silicates in the formulation of glycols (compositions) is detailed in these patents. In this technology, concentrated compositions of gelcole are typically produced and sold to end users who dilute the concentrated compositions with water and inject them into automobile radiators as coolants.

In the past, glycol-rich compositions using common corrosion inhibitors such as borax and silicates were known to have a tendency to form irreversible silicate gels when left in warehouses or shops for periods of time. . When an end user injects a glycol-rich composition into an automobile's radiator, it may not be easy to inject or liquid and lumps may come out due to the formation of slag or gel from the concentrated composition. The present invention was developed to eliminate this gel formation.

Wills on issued on April 17, 1979
No. 4,149,985 describes that gelation-resistant glycol compositions containing borate and silicate additives can be prepared; In the production of products, it was necessary to strictly control the order of addition of additives and the pHfc of the solution. This is difficult to control during manufacturing.

Wing, U.S. Pat. No. 4,287,077, issued September 1, 1981, describes gelation-resistant glycol compositions in which an effective amount of a polyoxyalkylene-functional silicone is added. ing. While these silicone compounds are certainly effective, the process for making glycol compositions containing these compounds requires the addition of alkali metal silicates, which are always added to glycol compositions to increase the corrosion resistance of the composition. The limitation is that these silicone compounds must be added before the process. The present invention is more effective in that the phosphorus-silane compound can be added at any time during the production of the composition.

British Patent No. 2,018,26 dated 17 October 1979
No. 6 A describes the use of alkali metal salts of polymers of silylalkylphosphonates as corrosion inhibitors for metals in alcoholic or glycolic compositions.

U.S. Pat. No. 4,333.843 issued June 6, 1982 to ffCWing et al.
-CCH2), n-Q-P(0) CCH3) -OR
chemical formula, where R is an alkyl group having 1 to 4 carbon atoms, n
A gelling-resistant glycol composition is described by using an effective amount of a hydrolyzate of a compound having an integer from 1 to 4, which hydrolyzate is identical to the polymer of the UK patent. Conceivable. However, since these polymers are expensive, there are severe restrictions on their use in commercial production.

Moreous published on February 18, 1964
U.S. Pat. No. 3,121,692 (columns 18 and 19) to E et al. describes gelation-resistant glycol composition formulations containing sodium silicate and aminosilanes. However, it has been found that the compound used in the present invention has far superior performance (kW) as an additive for preventing the formation of shigellum than the aminosilanes disclosed in the above-mentioned patents.

The following patents relate to storage-stable related compositions containing siloxanes, but do not disclose the use of alkali metal silicates, glycols, and anti-gelling agents.

U.S. Patent No. 3,234,144 (March 2, 1962)
Column 12 U.S. Patent No. 3,248,329 (April 26, 1966)
Column 19 U.S. Patent No. 3,312,622 (issued April 4, 1967) Columns 21 and 22 U.S. Patent No. 3,337,496 (issued April 22, 1967)
Column 9 U.S. Patent No. 3,341,469 (Published on
(Published September 12, 1967) Column 9 The present invention relates to a glycol composition having gelation resistance having the following composition.

(4) 85 to 98 wt% of alkylene glycol, alkylene glycol ether, or a mixture of both; ■
Effective amount for reducing corrosion of alkali metal silicates; (0 Effective amount of any of the following: (1) (RQ) 3-i (R1), 5i-R2-o
-P(Q)(QR")(R')(ff) [(1?I
:)) a, (R”)-Z-R2-o]2P(Q
) (R') mixture of onion zero valent I and and R2 is an aralkyl group having 7 to 10 carbon atoms, and R2 is an alkylene group having 1 to 4 carbon atoms.

The present invention also provides gelation resistance by adding to a glycol composition containing an alkali metal silicate or other corrosion inhibitor an effective amount to improve the gelation resistance of a compound represented by the formula: It covers all methods for producing glycol compositions.

(I) (Non-O) 3 one (R1) 5i-R2-0
-PCO)COR3)CR')(If) C(R□
)3. , CR1) mSi-R2-0]2PC (R4)
and (to) a mixture of ① and ①, where 鵠 is θ~2 R, 113r R' is an alkyl group having 1 to 4 carbon atoms R1
is an alkyl group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group having 7 to 10 carbon atoms, and R2 is an alkyl group having 1 to 4 carbon atoms.
~4 alkylene groups.

Examples of compounds falling within the range of I above where m is zero include methyl 3-(trimethoxysilyl)propyl methylphosphonate, butyl 2-()! J ethoxysilyl)ethylmethylphosphonate, propyl 3-(tripropoxysilyl)propylmethylphosphonate, and methyl 4-(tripropoxysilyl)butylmethylphosphonate.

Examples of compounds falling within the range of I above where m is 1 include methyl 3-(methyldimethoxysilyl)propylmethylphosphonate, methyl 3-(methyljethoxysilyl)propylmethylphosphonate, methyl 3-(dimethoxymethyl silyl) propyl ethyl phosphonate,
These include butyl 2-(dimethoxymethylsilyl)ethylmethylphosphonate, propyl 3-(dipropoxymethylsilyl)propylmethylphosphonate and methyl 4-(dimethoxymethylsilyl)butylethylphosphonate.

Examples of compounds falling within the above range (■) where m is 2 include methyl 3-(dimethylmethoxysilyl)glovylmethylphosphonate, methyl 3-(dimethylethoxysilyl)propylmethylphosphonate, and methyl 3-(dimethylmethoxysilyl)propylmethylphosphonate.
(methquindimethylsilyl)propylbutylphosphonate, butyl 2-(methoxydimethylsilyl)ethylethylphosphonate, propyl 3-(ethoxydiethylsilyl)propylmethylphosphonate, and ethyl 4-(
methoxydimethylsilyl)butylethylphosphonate.

Examples of compounds included in the above range (■) include bis-
[3-(trimethoxysilyl)propylcomethylphosphonate, bis-(2-()'Jmethoxysilyl)ethylcomethylphosphonate, bis-[3-(tripropoxysilyl)globil]methylphosphonate, bis-[4-
()rimethoxysilyl)butylcomethylphosphonate,
Bis-[3-(methyldimethoxysilyl)propylcomethylphosphonate, bis-[3-(methyl-jethoxysilyl5propyl)methylphosphonate, bis-[3-
(dimethylmethoxysilyl)propylcomethylphosphonate, and bis-[3-(dimethylethoxysilyl)
Propylcomethylphosphonate is present.

Examples of all mixtures falling within the above range (1) include the crude product of the reaction of one of trialkoxysilanes, dialkoxyalkylsilanes or alkoxydialkylsilanes having an omega haloalkylene group with a dialkylalkylphosphonate.

These compounds are listed in Phbed, June 6, 1978.
It can be prepared by the catalytic process shown in U.S. Pat. Other non-contact processes are shown below.

These gelling-resistant additives are compatible with other well-known corrosion inhibitors normally present in glycol compositions of this type, such as alkali metal borates, mercaptobenzotriazole compounds, nitrates, nitrites, phosphates and benzoates. It is effective even in the presence of acid salts.

The invention therefore relates to a single-phase composition of the following composition:
(a) 85-98 wt% of alkylene glycol, alkylene glycol ether, or a mixture of both; ■
Effective amount of alkyl metal silicate; (effective amount of any one of the following substances; (1) (R
O)3-O(R”), rlLSz-A!”-Q-P(O
) (OR38R').

(I[) ((Ro)a-JR”)R4-R2-O)
Z? (R'), or a mixture of valence I and group, phenyl group, carbon number 7-
10 aralkyl groups and R2 are alkylene groups having 1 to 4 carbon atoms.

Particularly preferred additive compounds are those having the following formula = (1) (RO) a S z-i CH2, 0-
PCO)CCH3)-OR.

(■) [(RO)3Si-+CH2 sending: 0-]2-P
(,0')CH3, or (to) A mixture of ■ and ■ Here, R is an alkyl group having 1 to 4 carbon atoms;
is an integer.

Glycols and glycol ethers that can be used in the present composition (1) Glycols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; (2) Glycol monoethers such as methyl, ethyl, propyl, and butyl ethers of ethylene glycol; , (3) glycol diethers such as methyl and ethyl diethers of ethylene glycol, diethylene glycol, and dipropylene glycol. Ethylene glycol, propylene glycol and the monomethyl ester of propylene glycol, ie methoxyglobanol, are particularly suitable.

All known corrosion inhibitors and additives used in combination with the above-mentioned silane in the present invention include, for example, alkali metal silicates such as sodium metasilicate, potassium metasilicate, lithium metasilicate, sodium tetraborate, Alkali metal borates such as potassium tetraborate, sodium metaborate, potassium metaborate, alkali metal salts of mercaptobenzothiazole, alkali metal salts of tolyltriazole, alkali metal nitrates such as sodium nitrate, potassium nitrate,
These include alkali metal nitrites such as sodium nitrite and potassium nitrite, alkali metal phosphates such as sodium phosphate and potassium phosphate, alkali metal benzoates, and various dyes.

In the process of making the compositions of the present invention, one or more of the above-mentioned glycols are added to the non-silicate corrosion inhibitors mentioned above and other inhibitors such as mercaptobenzothiazole, tolyltriazole, nitrates, phosphates, etc. necessary for corrosion protection. Mix with sufficient quantity.

The pH'x of the solution is then adjusted to the desired pH, ie a value of 5 to 12, preferably 8 to 11, by addition of an aqueous solution of an inorganic salt such as an alkali metal hydroxide, carbonate or phosphate. Furthermore, the above-mentioned alkali metal silicate is added to form a glycol composition having corrosion and gel resistance. The silane or mixture thereof can be added in full effective amount at any point during the manufacturing process.

Gelation resistance to achieve the purpose of the present invention! The effective amount of the silane that can result in a glycol composition of about 0.0
0.01 to 5.0 wt%, preferably 0.002 to 0.5 wt%, most preferably 0.005 to 0.2
The range is wt%.

Effective amounts for corrosion protection of the above-mentioned corrosion inhibitors are well known in the prior art and will of course depend on the respective additive. Generally, the amount of silicates and borates used is between 0.025 and 10% of the weight of the total solution.
wt%, borate 0.1 to 2. 0.05 to 0.5 wt% of silicate, preferably 0.05 to 0.5 wt% of silicate
The borate content ranges from 0.5 to 16 wt%.

In the present invention, the amount of borate added is preferably within the range (1,0
2.0wt%), the addition amount of silicate is within the desired addition amount range (0.025wt% to 0.3wt%).
t%). In each case, it is not possible to determine the exact amount of silicate, due to the complex effects with other corrosion inhibitors such as triazoles, nitrates, nitrites and phosphates mentioned above. .

Accelerated durability (aging) tests were conducted on Examples and Comparative Examples to compare and illustrate the gelation resistance of the compositions.

In the test, the glycol composition was placed in a constant temperature bath maintained at 80.90°C and 95°C, and the number of hours or days until gel formation was observed was measured.

The invention is illustrated by the following Preparation Methods, Examples and Comparative Examples.

Preparation method l.

3-chloropropyltrimethoxysilane 800ml in a 3 liter round bottom flask. Or (4 moles) and 1000.0 r (8 moles) of dimethylmethylphosphonate were added, and a reflux condenser was attached, and the mixture was heated to 1871:1 over 45 minutes while stirring with a magnetic stirrer. When a bubbler using mineral oil was attached to the outlet of the reflux condenser, gas generation was observed. The flask contents were held at 187° C. for an additional 722.5 hours, with no gas evolution observed, after which the reaction product was removed from heating and allowed to cool to room temperature. After cooling, a tan liquid of 1436.9F was obtained. Gas chromatographic analysis of this crude reaction product revealed the following composition: 44.4% dimethylmethylphosphonate: 39.6% methyl 3-(trimethoxysilyl)propylmethylphosphonate;
Two unidentified small peaks were observed at 7-2% bis-C3-()'Jmethoxysilyl)propylmethylphosphonate. One comes before dimethylmethylphosphonate and the other after bis-(I3-()rimethoxysilyl)globyl]methylphosphonate. A portion of this reaction product was heated to approximately 2 ttrm H? All unreacted dimethyl methyl phosphonate was recovered as a fraction at 30 to 50°C, and the fraction at 112 to 114°C was CH30 1 CH30-8iCH2CH2CII20POCH3 (10CH3CH3 It was identified as methoxysilyl)propylmethylphosphonate by gas chromatography, NMR and mass spectrometry.

Gas chromatographic analysis of the fraction at about 160 to 200°C revealed that this must be mainly bis-[3-()rimethoxysilyl)propylcomethylphosphonate of 0aJ3CH30CH3, according to US Pat. This was revealed by comparison with a standard sample prepared according to the method described in No. 4.093.641.

Examples 1 to 8 917, 25 wt% ethylene glycol solution of sodium metasilicate pentahydrate in ethylene glycol of (H')
．． (Added lk.

Sodium nitrate 33+aqueous solution (6,05')i was added and stirred until completely dissolved. Next, 2.05"k of a 50% aqueous solution of sodium tolyltriazole was added. Next, the pl-1 of the solution was adjusted to 8.4 to 8.5 using a 10% aqueous solution. Sodium metasilicate 5 An aqueous solution of the hydrate (LF'e dissolved in 10% of water) was added to the above mixture.

Table 1 shows the gel formation prevention properties (stability) of this solution and various stabilizers added at 80°C and 90'C.

However, the number of days of stability shown in Table 1 is the number of days until gel formation is first observed in the eye.

A consideration of the data presented in Table 1 shows that methyl 3
-(trimethoxysilyl)propylmethylphosphonate and bis-[:3-(trimethoxysilyl)propylcomethylphosphonate are 30'l)'I)m and 2
It is clear that even at a low concentration of 0 ppm, the additive is far more effective in increasing gel stability than the comparative example. The above-mentioned pure silane has no effect (although it cannot be overstated, the unpurified synthetic reaction mixture is also effective as an anti-gelling agent.

Examples 9-13 The examples herein demonstrate that phosphorus-modified silanes are effective in preventing gel formation even when added after addition of silicate and other corrosion inhibitors to all-glycol compositions. The stability of commercially available antifreeze solutions containing five types of silicate was evaluated at 95°C. Next, 0.02% of the unpurified synthetic reaction product f'jMl-compound shown in Preparation Method 1 was added to each sample, and the stability was evaluated under the same conditions. The results are shown in Table 2.

9 7 1 4.7
10 B O, 74, 111C
O,72,8 12D 1 5.713
E 1 4.7
Addition Examples 14-18° A certain commercially available antifreeze solution showed a stability value of 6 hours in a constant temperature bath at 95°C. By adding a small amount of methyl 3-(trimethylsilyl)propyl methylphosphonate to this unstable runt, the time to gel formation was significantly increased under the same conditions. The results are shown in Table 3.

Comparative example 00・25 14 20 21
5 50 216
100 217
200 10 Examples 19 and 20 Using the same procedure as shown in Examples 14-18, only the stabilizer added to certain commercially available antifreezes was changed to bis-[3-(trimethoxysilyl)propylcomethylphosphonate. It was carried out. In Example 19, bis-[3-()IJmethoxysilyl)propylmethylphosphonate 200p
The addition of pm improved the gel formation time from 6 hours to 6 days. In Example 20, the addition of 11,000 pp of the same compound resulted in a gel formation time of 14 days.

Examples 21 and 22 917, 25% ethylene glycol solution of sodium metaborate pentahydrate in ethylene glycol 52. O
Added 5'Y.

Sodium nitrate 33 + steamed rice aqueous solution (6, (1)'i added,
Stir until fully dissolved. Then 2.02 g of a 50% aqueous solution of sodium tolyltriazole was added. So 2
1) H'r of the solution using a 5 force aqueous solution.
It was adjusted to 8-5.9. Sodium metasilicate pentahydrate 1
:20. of water and added with stirring to form compositions with high and low silicate concentrations. Stability of these two solutions at 80°C and 90°C and methyl 3-() as a stabilizer in both! J methoxysilyl)propylmethylphosphonate 0.1%, i.e. 1
Table 4 shows the stabilization test results when 01000pp was added.

Table 4 (Comparative Example A) 0.5
2 121 (stabilizes A) 0.5
>24 >24 (Comparative example B)
0.7 1 1 From the above results,
A high concentration of sodium silicate (7000 ppm) results in a short gel formation time, but the use of the silane of the present invention increases the gel formation time. If the silicate concentration is low (5ooOppm
), the silane of the present invention makes the gel formation time extremely loud.

Examples 23 and 24 A sufficient amount of various stabilizers, each 50 ppm, was added to a commercially available silicate-containing antifreeze solution. The time required for visible silica gel to form in these θ solutions is 90 to 90%.
Measured at 5°C. The average gel formation times measured three times each are shown in Table 5.

Comparative example A None 3.0
Comparative Example B Phosphonate Functionality 7.
0 Sodium Salt of Siliconate (UK Patent No. 2,018,266A) Comparative Example C3-Aminopropyltrimethoxy 3.0 Silane (US Patent No. 3,121,692) 23 Methyl 3-()IJ Methoxysilyl) 7 ．．
7 Propyl methyl phosphonate 24 bis-[3-()rimethoxysilyl)8.
0propyl]methylphosphonate 188-

Claims (1)

[Claims] 1. Glycol composition having gelation resistance consisting of the following composition: (a) 85 to 98 wt% of alkylene glycol, alkylene glycol ether, or a mixture of both: [with] an alkali metal silicate; Effective amount for corrosion reduction; (
0 An effective amount of any of the following substances; (■) (RO)3-T1. , (R1), WLSi-R2
-O-P(O)(OR3)(R4)(I[) [(R
O) 3-0 (R1), rrLsi-R2-0] 2P('s (B 4 ), or (to) a mixture of ~4 alkyl groups, R1 is an alkyl group having 1 to 4 carbon atoms, a phenyl group and an aralkyl group having 7 to 10 carbon atoms, and R2 is an aralkyl group having 1 to 4 carbon atoms.
alkylene groups, . 2. The composition according to claim 1, wherein the alkylene glycol is ethylene glycol. 3. The composition according to claim 1, wherein the alkylene glycol is propylene glycol. 4. Claim 1, wherein the alkylene glycol ether is monomethyl ether of propylene glycol
composition of the term. 5. The composition of claim 1, wherein (2) is an alkylene glycol and an alkali metal borate in an effective amount to reduce corrosion. 6. The composition according to claim 5, wherein R is a methyl group and m is zero. 7. Adding to a glycol composition containing an alkali metal silicate and other corrosion inhibitors an effective amount to improve the gelation resistance of a substance of the formula 'ff: having a gelation resistance of Manufacturing method of glycol composition: (I) (first time) 3-? 7+, (R1) 5i-R2-0-
PC COR5) CR')(n) CCRO)3
--CR1)-8i-R2-O]2PCO)CR4),
'! Take (to) A mixture of (1) and (2) where m is 0 to 2 R, R3, and R' are alkyl groups having 1 to 4 carbon atoms R is an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a carbon number 7~
10 aralkyl groups and R4 are alkylene groups having 1 to 4 carbon atoms.