JPS60209547A - Polyol based on linear low molecular weight polyester - 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 is in the field of polyols based on certain linear low molecular weight polyesters having terminal primary hydroxyl groups, relatively low viscosity and relatively high solids content. belong to. The present invention also combines these polyols with cross-linking agents such as amino-triazine compounds and resins such as melamine-formaldehyde resins M, Urine S
- Coaches containing formaldehyde resins, epoxy resins, isocyanates, nates, or acrylic polymers containing reactive groups such as hydroxyl, carboxyl, amide, amine groups, etc. ,
"rA is also involved in the field of puffer fish compositions.

This application is filed under U.S. Pat. No. 4,018,848;
9,762.4,192,826.4゜222.911
．． and Fukoku Patent No. 1,561,076, all of which are hereby incorporated by reference.

The present invention relates to polyols based on linear, low molecular weight polyesters having terminal primary hydroxyl groups, relatively low viscosity and relatively high solids content. The invention also relates to a method for producing the polyol. The polyols of the present invention can be produced by transesterification of a mixture of alkyl esters of aliphatic dibasic acids or by esterification of the mixture of acids. Although it is preferred to start with methyl esters of adipic, glutaric and succinic acids, other lower alkyl esters such as ethyl, propyl and butyl esters can also be used; Because of the price factor, they are generally not given much consideration and no value is gained by their use.Moreover, this mixture of methyl esters is commercially available and is therefore all the more suitable for this reason. Commercially available methyl esters are approximately 0.5:1.5:
It has a molar ratio of dimethyl adipate, dimethyl glutarate and dimethyl succinate of 0.6. This molar ratio can be varied depending on the desired properties of the final product. For example, relatively high levels of glutarate result in relatively low viscosities. It is not necessarily limited to a mixture of three types of esters. If desired, it is also possible to use mixtures of two dibasic esters or one dibasic ester. The same applies to dibasic butyls, mixtures of acids or single compounds can be used. Dibasic acids which can be used are succinic acid, glutaric acid, adipic acid, pimelic acid, superic acid, azelaic acid and sebacic acid and their higher homologs or mixtures, often dibasic esters or simply DBE. These methyl esters, called esters, are IJ combined with diols or triols containing at least two primary hydroxyl groups. A preferred diol is cyclohexane dimetatool, CHDM. Examples of other diols and triols having primary hydroxyls that can be used include neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,2.6-t\
Xantriol, trimethylolethane, trimethylolpropane, ethylene glycol, diethylene glycol, dimethylolpropionic acid and 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3
-Hydroxypropionate and the like. Diols having a mixture of primary and secondary hydroxyls can also be used, including propylene glycol and 1,2-hexylene glycol. Mixtures of diols can also be used.

Catalysts are commonly used for esterification/transesterification reactions for the purpose of lowering the reaction temperature and reducing the color development of the product. Typical catalysts that can be used are alkoxides of titanium, soluble tin compounds such as dibutyltin dilaurate and soluble mankan compounds such as Mn(
OAc)2. Catalyst standards of 0.005-1.0 wt% can be used, typical standards are 0.01-0.1 wt%
It is.

In a preferred embodiment, the mixed methyl esters are combined with CHDM in a suitable reaction vessel and transesterified by heating in the presence of a common transesterification catalyst such as titanium alkoxide. - During the heating step the methanol is decomposed and it is easily removed in the form of M# methanol until the new reaction product is free or substantially completely free of methanol. The product produced generally contains some degree of unreacted cyclohexane dimetatool, depending on the initial molar ratio of the reactants and the technique used to remove the cyclohexanedimetatool. It probably contains. The initial starting molar ratios of dimethyl esters to cyclohexanedimethanol, which are also referred to as dibasic esters, taken as a whole and in part, are each about 1.
0=1.5 to 1.0+10.0, preferably about 1.0:2.0 to 1.0.4, respectively.
．． It is 0 seconds.

The final polyol produced will be completely free or substantially completely free of cyclohexane dimetatool. Totally free or substantially completely free refers to less than or equal to about 12% by weight, preferably about 4% by weight, based on the total weight of the final polyol reaction product.
The following means:

A common method used to remove unreacted diols is punch distillation. A preferred method uses continuous rapid striping of the CHDM followed immediately by means of cooling to prevent chemical reaction and equilibration. Continuous large scale rapid stripping can be carried out using several processes including continuous column distillation, multi-tube evaporators, and falling film evaporators - slipers. It is also contemplated that other methods such as liquid-liquid extraction or crystallization can be applied to remove excess diol.

A laboratory-scale method used to demonstrate the importance of rapid stripping and immediate cooling uses a rotary evaporator and oil bath. l at an absolute pressure of 1 to 2 torr and an oil bath temperature of 180 to 185 °C in a rotary evaporator.
:3 molar ratio of dibasic to cyclohexane dimetatool transesterification product over 8 minutes. 43% of the charge is evaporated and the product produced is at 25°C.
13' in, 800 cps viscosity and 98.8%
It had a solids content of 60 minutes.

If a patch distillation method is used, high viscosities and low solid gold* content will be obtained. The reason for these opposite results appears to arise from the chemical equilibrium of the products towards the most expected component distribution during slow patch distillation. In practice, for example, such patch polyesterification and transesterification reactions usually result in an equilibrium product distribution that is dictated by simple statistical considerations. Therefore, patch equilibration of high glycol to acid polyols or low glycol/acid molar ratios tends to give the same equilibrium product as would be obtained by carrying out the total transesterification reaction at the final molar ratio.

Surprisingly, wiped-f
ilm) C, HDM in a 3:1 molar ratio using an evaporator:
Rapid stripping and subsequent rapid cooling of the DBE polyester polyol feedstock removes approximately 35% of the total weight of the feedstock as CHDM and
It has been found to give products that combine low viscosities on the order of ,000 cps and high solids contents on the order of 98%.

In contrast, a typical punch distillation that removes the same weight of CHDM with or without rapid cooling has a
It gives a product with a much higher viscosity on the order of more than 18.000 cps at °C and a lower solids content on the order of 90%. These properties are of great importance in the formulation, application and performance of high-solids coatings such as those presented elsewhere in this application.

In principle, the same techniques can be applied as for other ester polyols. The greatest positive effect is obtained when all reactive groups have equal chemical reactivity. Therefore, a diol with one primary hydroxyl group and one secondary hydroxyl group will naturally have a secondary hydroxyl group since the primary will have reacted first to form the diester. will produce a lot of diesters. Furthermore, the secondary hydroxyl end groups are highly
Once the diester is formed, chain extension will be very difficult. In such cases, starting with a low diol:# ratio of 2:1 or less will give good yields of diester. For similar reasons, it should be possible to easily remove excess diol molecules without chain extension, resulting in very high solidity.

In one embodiment, a wiped-film evaporator is used to perform rapid stripping of CHDM.

A wiped-film evaporator, such as the Artisan Rototherm@ thin film evaporator, consists of a rotatable heated cylindrical part or heated cylindrical chamber with a feed inlet at the top above the drum; Or the raw material flows onto the drum. Top exit is CHDM
It's there for steam to escape. There is an outlet at the bottom through which the desired polyol product comes out. The rotatable drum has an electric motor that provides rotation. The temperature of the heated membrane is about 350 below and the absolute pressure is about 2
It is mm. The residence time of the substance to be treated is approximately 30
It varies from seconds to 2 minutes.

The product exiting the outlet passes through a heat exchanger where the product is cooled to about 200"F, after which it clears into a product storage vessel.

The polyols of the invention are cross-linking agents, such as polyisocyanates or aminotriazine-aldehydes,
Coating compositions without modification when combined with one or more substrates, such as melamine-formaldehyde resins, or urea-formaldehyde resins, such as those described in U.S. Pat. No. 2,197.357. Can be used as a class. U.S. Patent No. 3,663,389.
3.894.993 and 3,945. ．． Acrylic copolymers containing alcoholic hydroxy groups as shown in 961 with or without other reactive groups such as carboxyl groups, amido groups, amine groups, etc. can also be used. These patents are incorporated herein by reference.

Other common additives can also be used, such as pigments, touchstones, etc.

In order to provide a more complete understanding of the concept of the invention, the following examples are presented, in which all parts are by weight unless otherwise indicated. These examples are presented primarily for illustrative purposes and the specific illustrations of detail contained therein are not intended to limit the scope beyond that which is indicated in the claims. isn't it.

Into a suitable glass reactor the following ingredients were charged: 98.27 parts of CHDM (309.6 mol) 7.37 parts of DBE (20.9 mol).

12 while stirring the contents of the reactor using a mantle.
Heat to 5°C and then add 12.3 parts of titanium tetrabutoxide. Heating was continued while maintaining a flow of nitrogen in the reactor at rooml/min.

When the temperature reaches 160℃, keep the temperature at that standard,
Then 29 parts of DBE (82.2 mol) were metered into the reactor over a period of 3 hours with continuous stirring. Methanol vapor is continuously generated during the DBH addition period, which is cooled in a water-cooled glass condenser and
．． Four parts of liquid methanol were collected.

This product was transferred to a 1/4 square foot Artisan R
Processed in an ototherm wiped-film evaporator. The feed rate was 175°C product outlet temperature and ca.
It was set at 19 ml per minute at a pressure of Torr. Pass the product into the sifter outlet tube to bring the final product temperature to 95°C.
It was adjusted to

The product produced had a viscosity of 9000 cpS at 25°C and exhibited a solids content of 98% in a 1 hour test.

Example F illustrates the application of the invention.

A coating composition was prepared by mixing the following ingredients: Polyol from Example 1 60 Hexakis(methoxymethyl) Melamine (1) 4O n-Butanol 10 Flow modifier ( 2) 0,4 Mineral catalyst (3) 2% solids = 89.5 Viscosity = 880 cps (1) Cyme 1. '303', American e-Cyanamid Company (2) 3M Co, (Fluorocarbon) (3) + NgΦ Industries, Inc.-DNND
The coating is applied onto the phosphated steel panel with a coating rod to produce a film thickness of approximately 1 mil, which is then placed in a forced draft convection furnace and Cured under several conditions at different temperatures: Hours, minutes 20 15 10 5 Pencil hardness H-2) I H-28) l-2) 1) 1-
2H', heavy MEK friction 100 100 1QO100
Reverse Impact, Inches, Bond 804 [iQ+ 804 80 Point Rejection The following examples illustrate the improved coating properties obtained when the polyols of this invention are used as minor components of the binder system.

The following ingredients were combined in a suitable container.

Paper i Name 1 Acrylic resin (1) 200'280 240 Hexakis (methoxymethyl) Melamine (2) 25 50 6.0 Example 1
Polyols from - 10 20 isopropanol
25 42 44 Xylene -1838 DNNDSA (3) Amine shielding catalyst 2.5 4.0 4.0 Acrylic/melamine/polyol ratio 80/20/-80/30/1070/
2515 (1) Rohm and Haas Kai Company (2) Cy
mel 303, American 7e Cyanamide Life Company (3) King-Industries, Inc. The coating was applied onto the phosphated steel panel with a coating rod to yield a film thickness of approximately 1 mil, which was then forced Cured for 20 minutes at 150°C in a draft convection furnace. The properties are shown below.

1 2 3 Pencil hardness 2-38 4-582-3n Double MEK friction 100+100+100+ Adhesion loss, % 0 0 0 Impact, reverse 30-4080+80+ Direct ao+ eo+ 70/80 Water immersion 250 hours, 50°C Blistering rating Only 8 Very Only 8 Very Only 8 Aim A In this example, a pigmented enamel was prepared by grinding titanium dioxide in the polyol of the invention. The enamel thus produced had very high solidity and excellent low temperature curing properties as described below.

Combine 3 volumes of Ijsho coater: 550 parts of titanium oxide Polyol from Example 1 250 n-butanol 75 Cellosolve acetate dispersion on Cowles dissolver 125 Acrylic resin (1) 333 Hexakis (methoxymethyl) ) Melamine (2) 200 n-butanol 30 Solids, Dose % 80 Viscosity, cps 440 Polyol/Acrylic/Melamine 50150/40 (1) King Industries, Inc. (2) Cymel 303, American Fist Cyanamid
Company 11'', 1 enamel curing 2 hours, min +5 15 30 Temperature, °C, 121 93 82 Catalyst: DNNDSA, $TR5O, 62, 0, 2, 75 Pencil hardness 2-3HH-2HH-2n MEK Friction 200200170 Reverse God ■Clam 80+ 80+ 80+ Gloss, 60' 89 91 91 Immersed in water for 250 hours, 50°C Gloss, 60' 89 90 8B TRS-Total resin solidity side'' The polyol of Example 1 was mixed with an isocyanate cross-linking agent in the following manner. A room temperature curable coating composition was prepared by mixing with

Polyol of Example 1 100 Polyincyanate (1) 82 Xylene 30 2-Nitoxyethyl Acetate 30% Solids - 75 Viscosity - 60 seconds Ford 4 Cup Coating is sprayed onto the steel panel or coated with an applicator stick. It was applied to give membranous properties.

Coached panel 2411 at 2 temperatures! ″NIJ
.

Watching plants: Pencil hardness 5-6H Friction 200 Shock, reverse 160 inches, lbs. Direct 180 inch, bond The coating was no longer tacky after 6 hours.

(1) Mobay Chemical Co., Ltd. In the polyol of the present invention, n is 1 or 2. The amount of the ingredient in parentheses is at least 70% by weight when m is from 2 to 10. Approximately 300 to 600 such ingredients
Preferably, the molecular weight is sufficient to give a weight average molecular weight of between 4 and preferably between about 350 and 500. The final reaction molar ratio of dibasic acid to cyclohexanedimetatool is between about 1.0:1.7 and 1.0:2.3, respectively.

The method of the present invention provides a
about 150°C to 22°C for a period of 0 seconds to 10 minutes
Requires a stripping temperature of 5°C.

It is preferred to use a temperature of about 160° C. to 2.10° C. for a period of about 20 seconds to 2 minutes at about 0.1 to 2.00° C.

Patent Application King Industries φ Incocho Belletetted Procedure Correction Book January 14, 1981, Patent Office Secretary Shirakuden 1 Polyols based on low molecular weight polyesters 3
, Relationship with the case of the person making the amendment Patent applicant 4, agent 〒107 6. The scope of the patent claims subject to the amendment is revised as follows.

(1) has a terminal primary hydroxyl group, low viscosity, high solids content, and has a structural formula: [wherein n is 1 or 2 and at least 70% by weight is n-
1 and m=2-10] wherein the polyol is substantially free of cyclohexane dimetatool.

(2) The ratio of dibasic acid to cyclohexane dimetatool is approximately 1. Polyol according to claim 1, wherein O: between 1.7 and 1.0:23.

(3) The polyol of claim 1 having a weight average molecular weight of between about 300 and 600.

(4) The polyol of claim 1 having a weight average molecular weight of between about 350 and 500.

(5) has a terminal primary hydroxyl group, low viscosity, high solids content, and has a structural formula: where n is 1 but not 2 and at least 70% by weight n=
1 and 2-4] wherein the polyol is substantially free of cyclohexane dimetatool.

6. The polyol of claim 5, wherein the ratio of dibasic acid to cyclohexane dimetatool is between about 1.0:1.7 and 1.0:2.3, respectively.

(7) The polyol of claim 5, having a weight average molecular weight of between about 300 and 600.

(8) The polyol of claim 5, having a weight average molecular weight of between about 350 and 500.

(9) Esterification or transesterification of cyclohexane dimetatool with at least one aliphatic saturated dibasic acid or lower alkyl ester thereof in a molar ratio of from about 22:1.0 to about 2:1.0, respectively. The reaction was heated until substantially complete and the product thus produced was treated with O, O, to remove excess cyclohexane dimetatool.
for about 10 seconds to 10 seconds at an absolute pressure of 1 to 100)
sysstripping by using a product stripping temperature of about 150° C. to 225° C. for a period of time, thereby substantially removing cyclohexanedimetatool from the product produced, and removing the cyclohexanedimetatool from the product produced. A process for producing polyols, which consists in immediately cooling the polyol to prevent its chemical reaction.

(10) The method according to claim 9, wherein the stripping is performed using a continuous evaporator.

(il+) The method according to claim 9, wherein the stripping is carried out using a Wizoto film evaporator.

”

Claims (1)

Claims: (1) having a terminal primary hydroxyl group, low viscosity, high isoisomer content, and having the structural formula: [Formula--, where II is 1 or f is 2 and at least 70 tons; 11% has n=1 and m=2-io], where the polyol is substantially free of cyclohexane dimetatool, and is a linear, low molecular weight polyester. polyol based on. 2. The polyol of claim 1, wherein the ratio of dibasic acid to cyclohexane dimetatool is between about 1.0:1.7 and 1 O:2.3, respectively. (3) The polyol according to claim 1, which has a gravity average molecular weight of between about 300 and 600. (4) The polyol according to claim 1, having a position average molecular weight of between about 350 and 500. (5) Terminal primary hydroxyl group, low viscosity 1, ri
and has a structural formula: [wherein n is 1 or 2 and at least 70% of n
-'1 and m=2-4] wherein the polyol is substantially free of cyclohexane dimetatool. (8)': The polyol of claim 5, wherein the base acid cyclohexane dimetatool is between about 1.0:1.7 and 1.0:2.30, respectively. (7) The polyol of claim 5, having a weight average molecular weight of between about 300 and 600. (8) The polyol of claim 5, having a weight average molecular weight of between about 350 and 500. (9) cycloΔ, xane dimetatool with at least one aliphatic saturated dibasic acid or lower alkyl ester thereof in a ratio of about 1.0 to 2.2 to about 1 and 0 to 6, respectively;
The reaction is heated until the esterification or transesterification is substantially complete at a molar ratio of stripping by using a product stripping temperature of about 150° C. to 225° C. at pressure for about 10 seconds to 10 minutes, thereby substantially removing cyclohexane dimetatool from the product produced; A process for producing polyols, which consists in immediately cooling the produced product to prevent further chemical reactions. (10) The method according to claim 9, wherein the stripping is performed using a continuous evaporator. (11) The method according to claim 9, wherein the stripping is carried out using a wiped-film evaporator.