JPH02501830A - Neutralization of polyalkylene carbonate polyols for polyurethane prepolymer synthesis - 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] Polyalkylene carbonate polyol for polyurethane prepolymer synthesis neutralization of Polyurethane is the first thing that comes to mind when you think of foam products, and in fact polyurethane Letane dominates the solid form market. Such foams are also rigid. It can be either soft or soft, depending on the manufacturing method. In fact, polyurethane The system allows for major changes in polymerization and processing methods; This is the complexity of keeping the area suitable for foaming and foaming.

Like many polymers, polyurethanes, at least in principle, can be It is a common type of substance produced through However, industrial practicality, e.g. Based on feedstock availability and ease of processing (determined preferred method, e.g. Conventional condensation polymerization of bistaroloformates with amines yields polyurethanes, but on a large scale The implementation of this model requires the condensation of a diisocyanate and a diol (more generally A typical synthesis involves a diisocyanate and a polyol, where the diol is A special case, triols cause crosslinking). A typical example is 1,4-butane 2,4-toluene diisocyanate (TDI) that reacts with diols. fault In all cases, the practical problem is not at the level of individual chemical molecules, but rather Showing the physical manufacturing and molding process.

Polyurethane is quite difficult to process. Manufacture of good and effective forms is a continuous process involving precise control of the distribution and size of air pores or bubbles in the product. Closed cell foam is inadequate for making life preservers, while closed cell foam is It is insufficient for the production of Volume is indicated as a problem with polyurethane processing, and this Problems are generally within the scope of this invention excluding polymer stabilization.

Most polyurethanes are melted and molded using polyethylene. It cannot be easily injected into products.

One viable method is the "one-shot" method, whereby all reactants are are simultaneously mixed and injected into the molded part.

Another method involves controlling the synthesis of prepolymers, short-chain polyurethane intermediates. is necessary. The use of intermediates usually gives polyurethanes with better properties Ru. This prepolymer method is more forgiving than the one-shot method and allows hybridization However, current technology still has room for improvement. The present invention is based on prepolymer Concerning practical issues of stability.

In particular, the present invention relates to the treatment of polyols. This method produces a more stable prepolymer and processing of polyalkylene carbonate polyols leading to improved urethane products. including. Polyalkylene carbonate (PAC) polyols are suitable for base-catalyzed reactions. Some of the catalyst remains in the product PAC.

Therefore, the conventional technology uses residual acids in TDI to neutralize residual base species in polyols. depending on the species, e.g. HCl. If necessary, use TDI (always chloride) to neutralize. It is also possible to add acid chloride to benzoyl), but the limitation of conventional technology is that chloride Benzoyl does not stabilize the PAC prepolymer (if added in large amounts) even). Benzoyl chloride prevents the exothermic reaction from releasing, but residual chloride ions Same as HCl for many applications as it remains in the product (unsatisfactory). Benzoyl chloride does not give a stable prepolymer. The present invention has a longer storage time ( Stable P with two advantages: before processing) and longer gelation time (during processing) This produces an AC prepolymer. Therefore, early curing does not occur and the molded product is better. It has mechanical properties and environmental resistance.

PAC polyols are typically diols having an equivalent weight of about 250 to 20,000. However, triol may also be used. Addition of strong acid to PAC polyol neutralizes base catalyst and prevent side reactions including trimerization of TDI.

In particular, PAC polyols require initial characterization regarding their rcPRJ counts. Essential. rCPR, "controlled polymerization rate" indicating the amount of residual base in the prepolymer represents. CPR measurement is 0.0IN HC7! Methanol 100% for titration with Requires 30 g of PAC in m. "Urethane polyether prepolymer and Form: Effects of chemical and physical changes on reactions J, 5chotten , Shubmann and Ten Boor et al., J. Chem.

Ham, Vol. 5, No. 3, July 1960. The key point is negative CP due to the addition of strong acid. The goal is to obtain an R value. However, CPR values below -100 are harmful to the product. This is not necessary as it may lead to the opposite of the intended result.

The strong acids used are methanesulfonic acid (MSA) and p-)luenesulfonic acid. (PTSA) included. Experiment with each type of acid, although certainly many other strong acids will also work. It is desirable rather than to demonstrate the ability to clean PAC polyols. For example, as shown above, we tested to see if side effects occur. However, HCf was found to be an undesirable acid. But virtually any It is also clear that organic sulfonic acids work well.

Additionally, some acids, such as n, so, and PTSA, react directly with TDI and therefore PAC polyols need to be treated with acid before reaction with polyisocyanates. Ru.

This method can be used before reacting with the polyisocyanate to form a prepolymer. either later involves mixing the acid with the selected polyol, especially PAC.

Mix at 60@F (15°C) to 95”F (35°C) in a closed container. It is best to do so. Add the acid to the PAC with stirring. for mixing acids Stir the acid into the PAC using a stirrer. The amount of acid is quite small: for example PA The acid for Clf is the number 1) pRi, or an effective amount of just a few drops while stirring. Added. Since a small amount of acid is required, a neutral diluent (preferably PAC Add 10 to 50 parts of the polyol itself to the acid. Add the acid for a while while stirring. Add. If the residual base species in the PAC is known before treatment, the amount of acid is I can calculate it. On the other hand, acid is added in proportion to neutralize the base and avoid overdosing. It will be done. Therefore, the preferred method is to stir the PAC until the necessary neutralization is achieved. This is done by adding acid. The degree of acid addition depends primarily on the degree of PAC neutralization.

If the acid addition is insufficient, it may be necessary to repeat the process until a negative CPR value is obtained.

The following examples and comparative experiments are intended to illustrate the invention and limit its scope. isn't it.

North China Flame Cunning This comparative experiment shows the ineffectiveness of benzyl chloride as a stabilizer. PAC poly toluene diisocyanate containing 5% isocyanate. A prepolymer having an amount of The CPR value of this prepolymer was calculated using the above method. So I investigated. Brookfield viscometer model to measure the viscosity of prepolymer after processing Measured by RVTD and expressed in centipoise. This machine is a rotating machine containing many spindles. It is a viscometer. The spindle is placed in the solution to be analyzed and rotated. appropriate speed Calculate viscosity by multiplying the calibration factor by RPM.

Table 1 1.76 instantaneous 1.40 74.200 (74,2) 1 hour 0,99 40.400 (40 ,4) 1 day 0.006 33,000 (33) 1 day - 2,0127,000 (27) 1st to 2nd day - 4,9824,000 (24) 1st to 2nd day - 7,9529 ,800 (29,8) 1-2 days - 13,8941,200 (41,2) 1-2 2nd day - 31,3537,000 (37) 1st to 2nd day - 61,4126,800 ( 26,8) Various side reactions including trimerization resulting in isocyanate gelation for 1 to 2 days It is thought that a reaction occurred.

±− top In the second test described in Table H, PTSA was used to treat a fixed amount of PAC. Using. The treated PAC is then reacted with excess toluene diisocyanate, A prepolymer containing 5 percent isocyanate groups was formed. Measures 80' C after 24 hours.

Table■ 0.2 No gelation (remains liquid) -5,0 No gelation (remains liquid) The first two experiments show trimerization of TDI, while the bottom two experiments show the trimerization of TDI, while the bottom two experiments show the trimerization of TDI In the third test shown in Table ■, which shows the stability of the prepolymer made of AC, the %NCO loss More quantitative data by measuring loss (weight percent of prepolymer) Obtained. This percentage is calculated by performing the dibutylamine reaction followed by backdropping with HCI. Measured by Measurements were taken after 24 hours at 80''C.

6.0 Benzyl chloride gelation -10PTSA 0.04 1.7? ISA　0.01 Treatment of the polyol in the latter two cases or neutralization of the Haffle polymer Enough to stop quantification.

As shown in the table above, PAC polyol neutralization yields a more effective prepolymer. It is done for the purpose of

Submission of translation of written amendment (Article 184-8 of the Patent Act) August I, 1999 Yoshi, Commissioner of the Patent Office 1) Takeshi Moon 1 Display of patent application PCT/US88100285 2 Name of the invention Address: Michigan, USA 48640. Midland.

Aposite Road, Dow Center 2030 people Name: The Dow Chemical Company Npanee 4 agent Amended claims 1. Add an effective amount of acid to the polyalkylene carbonate polyol to obtain a stabilized polyalkylene carbonate polyol. The preparation of a prepolymer comprising the step of adding it to a lekylene carbonate polyol. formulation method.

2. The method according to claim 1, wherein the acid is an organic sulfonic acid.

3. The method according to claim 2, wherein the addition of acid is carried out until a negatively controlled polymerization rate is obtained. .

4. Claim 3, wherein the acid is p-)luenesulfonic acid or methanesulfonic acid. How to put it on.

5. The method of claim 1, wherein the acid is added with stirring.

6. Negative control polymerization rate was measured for polyalkylene carbonate polyol. 6. The method of claim 5, wherein the step of adding acid is repeated until the acid is added.

7. The method of claim 5, wherein the stirring is carried out at ambient temperature.

8. The method according to claim 7, wherein the stirring is performed in a closed container.

9. Mix the acid with the diluent before adding it to the polyalkylene carbonate polyol. 6. The method according to claim 5.

10. The method according to claim 1, wherein the acid is added before the preparation of the prepolymer.

11. The method of claim 1, wherein the acid is added after the prepolymer is prepared.

12. A product produced by carrying out the method of claim 5.

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Claims (13)

[Claims] 1. Add an effective amount of acid to the polyalkylene carbonate polyol to obtain a stabilized polyalkylene carbonate polyol. The preparation of a prepolymer comprising the step of adding it to a lekylene carbonate polyol. formulation method. 2. 2. The method of claim 1, wherein the acid is an organic sulfonic acid. 3. 3. A process according to claim 2, wherein the addition of acid is carried out until a negatively controlled polymerization rate is obtained. 4. Claim 3, wherein the acid is p-toluenesulfonic acid or methanesulfonic acid. How to put it on. 5. 2. The method of claim 1, wherein the acid is added proportionately with stirring. 6. Negatively controlled polymerization rates were measured for polyalkylene carbonate polyols. 6. The method of claim 5, wherein the step of adding acid is repeated until the acid is added. 7. 6. A method according to claim 5, wherein the stirring is carried out at ambient temperature. 8. 6. The method according to claim 5, wherein the stirring is carried out using a stirring device. 9. 9. The method according to claim 8, wherein the stirring is carried out in a closed container. 10. Mix the acid with the diluent before adding it to the polyalkylene carbonate polyol. 6. The method according to claim 5. 11. 2. A method according to claim 1, wherein the acid is added before the preparation of the prepolymer. 12. 2. The method of claim 1, wherein the acid is added after the prepolymer is produced. 13. A product produced by carrying out the method according to claim 5.