CN1500771A - Plasticizer used for polyvinyl butyral - Google Patents
Plasticizer used for polyvinyl butyral Download PDFInfo
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- CN1500771A CN1500771A CNA021522162A CN02152216A CN1500771A CN 1500771 A CN1500771 A CN 1500771A CN A021522162 A CNA021522162 A CN A021522162A CN 02152216 A CN02152216 A CN 02152216A CN 1500771 A CN1500771 A CN 1500771A
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Abstract
The plasticizer for polyvinyl butyral is alkyl diacid bis(alkyl diethanediol) ester with the structural expression of R-(O-CH2-CH2)2-O-C(=O)-(CH2)nC(=O)-O-(CH2-CH2-O-)2-R, where R is C1-C10 alkyl group and n is integral of 4-6. The plasticizer for polyvinyl butyral has low volatility, excellent compatibility with polyvinyl butyral resin and thus excellent machinability. The adhered glass made with the plasticizer and polyvinyl butyral has excellent excellent mechanical performance, and may be used automobile, building and other area needing adhered glass.
Description
Technical Field
The present invention relates to a plasticizer for polyvinyl butyral, which is a di (alkyl diethylene glycol) alkanedioate having the following structural formula (I):
R-(O-CH2-CH2)2-O-C(＝O)-(CH2)n-C(＝O)-O-(CH2-CH2-O-)2-R (I)
wherein R, which may be the same or different, represents C1-10An alkyl group;
n represents an integer of 4 to 6.
Background
Polyvinyl butyral films have been widely used for bonding single or multiple layers of glass to improve the penetration resistance of the glass by dissipating external forces. Typical polyvinyl butyral films provide satisfactory mechanical properties and film processability through plasticizers.
In the process of glass bonding or film production, prevention of plasticizer volatilization is an important issue because volatile plasticizers are liable to cause danger in the process of glass bonding or film production, and therefore, it is necessary to select plasticizers having low volatility.
The compatibility of polyvinyl butyral with the plasticizers contained therein is related to the edge stability (edge stability) of the bonded glass. The edge stability of the bonded glass made using a plasticizer compatible with polyvinyl butyral is superior to the bonded glass made using a plasticizer incompatible with polyvinyl butyral. The choice of a plasticizer compatible with polyvinyl butyral is therefore an important factor in obtaining a bonded glass with good edge dimensional stability.
Polyvinyl butyral films are widely used in the manufacture of single or multiple ply bonded glass. Plasticizers used in the manufacture of polyvinyl butyral films are typically polyol or polyacid esterified plasticizers and include, for example, triethylene glycol di-n-heptanoate (3G7), tetraethylene glycol di-n-heptanoate (4G7), dihexyl adipate (DHA), triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4GO), triethylene glycol di-2-ethylbutyrate (3GH). The plasticizers are products of esterification reaction of polyhydric alcohol except DHA.
However, when these plasticizers are poor in compatibility with polyvinyl butyral, a large amount of plasticizer cannot be used in combination, or there is a problem that the plasticizer bleeds out, and when the amount of plasticizer is too small, physical properties of the processed film are not suitable as an interlayer for bonding glass in addition to the effect on processing. Since a high concentration of plasticizer is generally required in a film having excellent physical properties, there is still a need for a plasticizer having improved compatibility with polyvinyl butyral.
The present inventors have conducted extensive studies on a plasticizer for polyvinyl butyral based on the above problems, thereby completing the present invention.
Object of the Invention
The first object of the present invention is to provide a novel plasticizer for di (alkyl diethylene glycol) alkanedioic acid esters which has a high boiling point, low volatility and good compatibility with polyvinyl butyral.
The second object of the present invention relates to a polyvinyl butyral composition comprising polyvinyl butyral and the bis (alkyl diethylene glycol) alkanedioate plasticizer of the present invention.
Detailed Description
The novel plasticizers of the bis (alkyl diethylene glycol) alkanedioic acid esters of the present invention have the following structural formula (I):
R-(O-CH2-CH2)2-O-C(＝O)-(CH2)n-C(＝O)-O-(CH2-CH2-O-)2-R (I)
wherein R, which may be the same or different, represents C1-10An alkyl group;
n represents an integer of 4 to 6.
The di (alkyl diethylene glycol) alkanedioate plasticizer according to the present invention is different from plasticizers conventionally used for polyvinyl butyral in that the di (alkyl diethylene glycol) alkanedioate according to the present invention has an ether functional group at the terminal.
R does not denote "C1-10Alkyl "represents a straight or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples thereof include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, octylpentyl, isopentyl, n-hexyl, isohexyl, heptyl, octyl, nonyl, decyl and their isomeric groups.
Alkanedioic acids di (C) of the present inventionAlkyl diethylene glycol) esters from C6-8The alkane diacid and the diethylene glycol monoalkyl ether are subjected to polybasic acid esterification reaction in the presence of a catalyst to obtain the catalyst. The reaction formula is as follows:
wherein R and n are as defined above.
C used in the present invention6-8Examples of alkanedioic acids include, but are not limited to, adipic acid, pimelic acid, suberic acid, and the like, for example.
The hydroxyl group content of the polyvinyl butyral is out of a certain range not compatible with too much plasticizer, and when the plasticizer does not plasticize the polyvinyl butyral effectively, the resulting polyvinyl butyral film will not dissipate external impact force, thereby adversely affecting the bonded glass. Thus, good compatibility with polyvinyl butyral and satisfactory physical properties are required for excellent plasticizers for polyvinyl butyral, and the hydroxyl group content of polyvinyl butyral is generally limited to a specific small range in consideration of plasticizer compatibility.
However, according to the present invention, since the di (alkyl diethylene glycol) alkanedioate plasticizer of the present invention has good compatibility with polyvinyl butyral, a polyvinyl butyral film having excellent physical properties can be obtained even when the hydroxyl group content of polyvinyl butyral is in a wide range. For example, polyvinyl butyral having a hydroxyl group content in a wide range of 15 to 30 wt% can still obtain a polyvinyl butyral film having excellent strength when the bis (alkyl diethylene glycol) alkanedioate of the present invention is used as a plasticizer.
Another object of the present invention relates to a polyvinyl butyral composition comprising 100 parts by weight of polyvinyl butyral and 15 to 55 parts by weight of the bis (alkyl diethylene glycol) alkanedioate according to the invention. Preferably, the polyvinyl butyral comprises 100 parts by weight of polyvinyl butyral and 20 to 50 parts by weight of the bis (alkyl diethylene glycol) alkanedioate of the present invention. Most preferably, the polyvinyl butyral comprises 100 parts by weight of polyvinyl butyral and 30 to 45 parts by weight of the di (alkyl diethylene glycol) alkanedioate of the present invention.
The preparation of the polyvinyl butyrals used in the invention, which is known to the person skilled in the art and is therefore not intended to limit the scope of the present invention, can be carried out by condensation reaction of polyvinyl alcohol having an average degree of polymerization of from about 800 to 3000, preferably an average degree of polymerization of from 1000 to 2500, with butyraldehyde in the presence of a catalyst.
The hydroxyl group content of the polyvinyl butyral used in the present invention obtained by the above process is 15 to 30 wt%, preferably 15 to 25 wt%, most preferably 19 to 24 wt%.
The polyvinyl butyral composition of the present invention may also contain other additives, and these additives are not particularly limited as long as the properties of the film made of the composition are not adversely affected. Non-limiting specific examples thereof include, for example, ultraviolet absorbers such as benzotriazole series, adhesion control agents such as alkali metal or alkaline earth metal formates, and antioxidants, etc.
The present invention will be described in more detail with reference to the following examples and comparative examples. These examples are intended to illustrate preferred embodiments of the invention only and are not intended to limit the scope of the invention. Various modifications will be apparent to those skilled in the art from this detailed description of the invention. Such modifications are intended to be included within the scope of this invention without departing from the spirit and scope thereof.
In the following examples and comparative examples of the present invention, the physical and chemical properties of the alkanedioic acid di (alkyl diethylene glycol) ester plasticizer of the present invention and the properties of the film made of the plasticizer and polyvinyl butyral were measured using the following methods.
A. Cloud point (compatibility): 5.6 g of polyvinyl butyral resin was dissolved in 70 g of plasticizer, the temperature was raised to 150 ℃ to form a clear solution, and then the clear solution was slowly cooled, and the temperature at which the solution began to turn white and fog was recorded, which was the fog point. A lower haze point indicates better compatibility of the two components.
B. Polymerization degree of polyvinyl alcohol: measured by the method of JIS K6726. About 10 g of polyvinyl alcohol was placed in a 300 ml Erlenmeyer flask, and 200 ml of methanol and 3 ml of 12.5N NaOH were added. After mixing well, the mixture was placed in a water bath at 40 ℃ and reacted well for 1 hour until no acetate group was present. After the reaction, NaOH and NaOAc were washed with methanol until the washing solution was neutral, to obtain polyvinyl alcohol. The polyvinyl alcohol which is alkalized and washed clean is placed on the surface of the glass and is moved to an oven with the temperature of 105 ℃ for full drying. After cooling, the mixture was filtered through filter paper. And (3) sucking 20 ml of filtrate by using a 20 ml pipette into an evaporating dish, and drying the evaporating dish in a constant-temperature oven at the temperature of 105 +/-2 ℃ until the weight is constant.
Cy (concentration, g/l) is the weight gain of the evaporation dish x 50
10 ml of the filtrate was taken up by a 10 ml pipette in an Ostwald viscometer and placed in constant temperature water at 30. + -. 0.1 ℃ and then the number of seconds it fell through the two markings was measured and recorded as T1. The number of seconds it fell between two markings was measured using distilled water as a blank and recorded as T0. The degree of polymerization (Dp) was calculated with the following procedure:
log Dp＝1.613 logμ×104/8.29
wherein mu (limiting viscosity) is 2.303 log murel/Cy
μrel(relative viscosity) ═ T1/T0
C. Hydroxyl group content of polyvinyl butyral: measured using the method described in JIS K6728. 0.4 g of polyvinyl butyral is weighed out accuratelyin a covered triangular flask and 10 ml of pyridine-acetic anhydride solution is added. And (3) installing a reflux condenser tube, carrying out full reflux reaction for 2 hours, cooling, adding 20 ml of 1, 2-dichloroethane above the condenser tube, fully stirring, adding 50 ml of deionized water, uniformly mixing, and standing for 30 minutes. 3 drops of phenolphthalein indicator are added dropwise, and the final point is obtained by titration with 0.5N NaOH until reddish color appears. The number of titrated milliliters of 0.5N NaOH was recorded (a). A blank test was also run and the number of milliliters titrated with 0.5N NaOH was recorded (b). The hydroxyl content was calculated as follows:
hydroxyl weight percent (b-a) multiplied by f multiplied by 220.25/sample weight
Wherein f is 0.5N NaOH factor (factor)
Example 1: preparation of polyvinylbutyrals
1000 kg of polyvinyl alcohol (degree of polymerization 1780) was dissolved in 9000 l of water by heating, the solution was cooled to 16 ℃ and 115 kg of 35 wt% hydrochloric acid and 585 kg of butyraldehyde were added to carry out a condensation reaction, which was maintained at 16 ℃ until polyvinyl butyral precipitated. Then the temperature was raised to 60 ℃. The reaction mixture was maintained at 60 ℃ for 3 hours and stirred to complete the reaction. The polyvinyl butyral precipitate was washed with deionized water and dried in a dryer to obtain polyvinyl butyral having a hydroxyl content of 18.5 wt%.
Example 2: preparation of polyvinylbutyrals
According to the same method as in example 1, but with 572 kg of butylaldehyde in place of the amount of butylaldehyde in example 1, polyvinyl butyral having a hydroxyl group content of 20.2% by weight was obtained.
Example 3: preparation of polyvinylbutyrals
According to the same method as example 1, but with 548 kg of butyraldehyde instead of the amount of butyraldehyde in example 1, a polyvinyl butyral having a hydroxyl group content of 22.2% by weight was obtained.
Example 4: preparation of polyvinylbutyrals
According to the same method as in example 1, but with 555 kg of butylaldehyde instead of the amount of butylaldehyde in example 1, a polyvinyl butyral having a hydroxyl group content of 21.4% by weight was obtained.
Example 5: preparation of alkanedioic acid di (alkylglycol) esters
Adipic acid and diethylene glycol butyl ether (molar ratio 1: 2.3) were continuously added to the reactor, and 620 g in total of adipic acid and 1580 g in total of diethylene glycol butyl ether were added to the reactor, and after uniform mixing, a titanium metal catalyst (product number D600 available from changchun artificial resins works ltd) was added to perform a deoxidation reaction. In N2The temperature is raised and the water is dehydrated in the environment, and then the reaction is carried out for about 10 hours at 220 ℃. After completion of the reaction, unreacted diethylene glycol butyl ether was recovered and the product was purified to obtain 1852 g of di (butyl glycol) adipate.
Examples 6 to 7: preparation of alkanedioic acid di (alkylglycol) esters
In a similar manner to example 5, but replacing adipic acid with pimelic acid and suberic acid, respectively, pimelic acid di (butyl glycol) ester and suberic acid di (butyl glycol) ester were obtained, respectively.
Examples 1 to 3
The polyvinyl butyrals of examples 1 to 3 were each subjected to a haze point test with a di (butyldiglycol) adipate plasticizer, and the results are shownin Table 1.
Comparative examples 1 to 3
The polyvinyl butyrals of examples 1 to 3 were subjected to the cloud point test with dihexyl oxalate (DHA) plasticizer, respectively, and the results are shown in Table 1.
Comparative examples 4 to 6
The polyvinyl butyrals of examples 1 to 3 were subjected to the haze point test with the plasticizer tetraethylene glycol di-n-heptanoate (4G7), respectively, and the results are shown in Table 1.
TABLE 1
| Hydroxyl content (wt%) of polyvinyl butyral | Cloud point deg.C | |
| Example 1 | 18.5 | 90 |
| Example 2 | 20.2 | 80 |
| Example 3 | 22.2 | 98 |
| Comparative example 1 | 18.5 | 93 |
| Comparative example 2 | 20.2 | 87 |
| Comparative example 3 | 22.2 | 110 |
| Comparative example 4 | 18.5 | 131 |
| Comparative example 5 | 20.2 | 139 |
| Comparative example 6 | 22.2 | 142 |
The results in table 1 show that the di (butyldiglycol) adipate plasticizer of the present invention is more compatible with the polyvinyl butyral resin than DHA and 4G 7. The better compatibility means that the film is less likely to undergo phase separation after processing and therefore has poor properties.
Example 4
100 parts by weight of the polyvinyl butyral resin obtained in example 4 were mixed with 35 parts by weight of di (butyl glycol) adipate in a high intensity mixer. The plasticized heterogeneous polyvinyl butyral mixture is melted in an extruder and the melt is forced through a film-forming die. Melt temperature was about 195 ℃ and extruded into about 0.76 mm sheets.
The resulting polyvinyl butyral sheet was placed between two flat glasses (30 cm long by 30 cm wide by 3 mm thick). The bonded glass was placed in a rubber bag and evacuated to a vacuum of 20mm Hg for 20 minutes to remove air. The bag was placed in an autoclave at 90 ℃ for 30 minutes. The autoclave temperature was raised to 140 ℃ and the pressure to 12 liters per square centimeter for 20 minutes. And (3) cooling the autoclave to below 50 ℃, and then decompressing to obtain the bonded glass.
The tensile strength, compatibility, thermal weight loss rate and flow rate of the polyvinyl butyral film were measured in the following methods. The edge dimensional stability and penetration resistance of the resulting bonded glass were measured in the following manner. The results are shown in Table 2.
D. Tensile strength: test pieces were prepared according to the method of ASTM D638, and the polyvinyl butyral films were kept at 20.6 ℃ and 23.5% relative humidity for 48 hours before the test. The test pieces were testedin a universal tester at a tensile speed of 200 mm/min. The tensile strength at break of the test piece was recorded.
E. Compatibility: the polyvinyl butyral film is sandwiched between two pieces of oil absorption paper, and the oil absorption paper is placed in a relative humidity of 100% and 0 ℃ for 72 hours, and whether the plasticizer bleeds out or not is observed, if the plasticizer bleeds out, the plasticizer is incompatible, and otherwise, the plasticizer is compatible.
F. Thermogravimetric loss rate: the polyvinyl butyral film was placed in an oven at 150 ℃ for 1 hour, and the heat weight loss rate of the film was measured.
G. Flow rate: the test was carried out according to ASTM D1238, test temperature 150 ℃ and load 5000 g.
H. Edge dimensional stability: the prepared bonded glass was placed in an environment of 80 ℃ and 95% relative humidity for 2 weeks, and the distance of whitening of the edge of the bonded glass was observed.
I. Penetration resistance test: the bonded glass was held at 21 ℃ for 4 hours before testing. An electromagnetic ball drop tester was used to drop a 2.27 kg steel ball from a height of 4 m to impact the bonded glass and to check whether the steel ball penetrated the bonded glass.
Comparative example 7
The same procedure as in example 4 was followed, except that 35 parts of DHA were used instead of 35 parts of di (butyldiglycol) adipate. And the properties of the film and the bonded glass were tested as described in example 4. The results are shown in Table 2.
Comparative example 8
The same procedure as in example 4 was followed, except that 35 parts of bis (butyldiglycol) adipate was replaced with 35 parts of 4G 7. And the properties ofthe film and the bonded glass were tested as described in example 4. The results are shown in Table 2.
TABLE 2
| Example 4 | Comparative example 7 | Comparative example 8 | |
| Thermogravimetric loss ratio (%) | 1.08 | 4.51 | 1.45 |
| Tensile strength (Mpa) | 37.1 | 31.7 | 36.5 |
| Elongation (%) | 410 | 365 | 395 |
| Flow Rate (g/10 min) | 1.5 | 1.3 | 1.5 |
| Edge dimensional stability (mm) | 2 | 8 | 2 |
| Penetration resistance | Does not penetrate through | Penetration | Does not penetrate through |
| Compatibility | Compatibility of | Incompatibility | Compatibility of |
As can be seen from table 2, the polyvinyl butyral film produced by using the bis (butyldiglycol) adipate plasticizer of the present invention has excellent mechanical properties, and the heat weight loss rate thereof is lowerthan that of DHA and 4G7, which contributes to the safety improvement of the film processing and glass bonding process, and the bonded glass produced has excellent penetration resistance and edge dimensional stability.
Claims (13)
1. A bis (alkyl diethylene glycol) alkanedioic acid ester of the following formula (I),
R-(O-CH2-CH2)2-O-C(＝O)-(CH2)n-C(＝O)-O-(CH2-CH2-O-)2-R (I)
wherein R, which may be the same or different, represents C1-10An alkyl group;
n represents an integer of 4 to 6.
2. The di (alkyl diethylene glycol) alkanedioate according to claim 1, for use as a plasticizer.
3. The di (alkyl diethylene glycol) alkanedioate according to claim 2, for use as plasticizer for polyvinyl butyral.
4. The bis (alkyldiethylene glycol) alkanedioate of claim 1, wherein R is C1-6An alkyl group.
5. The di (alkyldiethylene glycol) alkanedioate according to claim 4, which is di (butylglycol) adipate.
6. A polyvinyl butyral composition comprising 100 parts by weight of polyvinyl butyral and 15 to 55 parts by weight of the bis (alkyl diethylene glycol) alkanedioate according to claim 1.
7. The polyvinyl butyral composition according to claim 6, comprising 100 parts by weight of polyvinyl butyral and 20 to 50 parts by weight of the bis (alkyl diethylene glycol) alkanedioate according to claim 1.
8. The polyvinyl butyral composition according to claim 7, comprising 100 parts by weight of polyvinyl butyral and 30 to 45 parts by weight of the bis (alkyl diethylene glycol) alkanedioate according to claim 1.
9. The polyvinyl butyral composition according to claim 6, wherein the hydroxyl content of the polyvinyl butyral is 15 to 30 wt%.
10. The polyvinyl butyral composition according to claim 9, wherein the hydroxyl content of the polyvinyl butyral is 15 to 25 wt%.
11. The polyvinyl butyral composition according to claim 10, wherein the hydroxyl content of the polyvinyl butyral is 19 to 24 wt%.
12. A polyvinyl butyral composition as claimed in any one of claims 6 to 11 for use in the production of bonded glass.
13. A polyvinyl butyral composition as claimed in any one of claims 6 to 11, for use in the production of bonded glass in the automotive industry, in the building sector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02152216 CN1221519C (en) | 2002-11-19 | 2002-11-19 | Plasticizer used for polyvinyl butyral |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02152216 CN1221519C (en) | 2002-11-19 | 2002-11-19 | Plasticizer used for polyvinyl butyral |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1500771A true CN1500771A (en) | 2004-06-02 |
| CN1221519C CN1221519C (en) | 2005-10-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02152216 Expired - Lifetime CN1221519C (en) | 2002-11-19 | 2002-11-19 | Plasticizer used for polyvinyl butyral |
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- 2002-11-19 CN CN 02152216 patent/CN1221519C/en not_active Expired - Lifetime
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