High-molecular cross-linked polyvinyl butyrals, method for their preparing and their applying

FIELD: organic chemistry, polymers, chemical technology.

SUBSTANCE: invention relates to new high-molecular cross-linked polyvinyl butyrals, to a method for their synthesis and to their applying also. Invention describes high-molecular cross-linked polyvinyl butyrals prepared by cross-linking polyvinyl butyral with diethyl- and/or dimethyl oxalate. Method for preparing indicated polyvinyl butyrals involves addition of a cross-linking agent and, if necessary, a plasticizing agent to the parent polyvinyl butyral, homogenization of the mixture and thermal cross-linking at temperature from 80°C to 280°C. Polyvinyl butyrals prepared by such method are components of films useful for manufacturing the triplex. Films made by using such polyvinyl butyrals show the rupture strength value at the level 29 N/mm2 and glasses made of such films show stability against the impact in F- and Sn-directions as 8 and 4, respectively.

EFFECT: improved preparing method, improved and valuable properties of films.

9 cl, 2 dwg, 13 ex

 

This invention relates to new high molecular weight cross-linked polyvinylbutyral, method of their production and their use.

It is known that polyvinylbutyral together with plasticizers by extrusion processed into films, especially those used in triplexes.

To increase the molecular weight of such polyvinylbutyral in the application EP-A-0211818 features knit polyvinylbutyral through sustainable intermolecular diacetylenic links. When this binding occurs with aldehydes at least two aldehyde groups. When this substance, forming a cross connection, before or during acetalization polyvinyl alcohol add oil aldehyde.

However, the stitching polyvinylbutyral dialdehyde because of the high reactivity of aldehydes leads to the formation of highly crosslinked, very high molecular weight and therefore partially insoluble polyvinylbutyral. In addition, the crosslinking reaction due to the small selectivity difficult is controlled, resulting ensure reproducible quality of the product is very difficult.

Thus, the objective of the invention is to obtain polyvinylbutyral, which are characterized by higher mechanical strength than unstitched products, and how to obtain them, over tor is, is repeatable.

Unexpectedly, it was shown that high molecular weight polyvinylbutyral can be reproducibly obtained by crosslinking di - and/or polycarboxylic acids or their esters.

Thus, an object of the present invention are high molecular weight cross-linked polyvinylbutyral obtained by crosslinking polyvinyl butyral at least one di - and/or polycarboxylic acid or their derivatives, preferably their esters, as cross-linking agent.

Preferred crosslinking agents are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, taconova acid, phthalic acid, terephthalic acid, and their esters.

Particularly preferred crosslinking agents are aliphatic diesters of formula (I)

ROOC-(CH2)n-COOR (I)

in which the residues R independently of one another denote the same or different With1-C4-alkali and n=0-4, preferably n=0.

Especially using diethyl - and/or dimethyloxalate.

Thus, stitched polyvinylbutyral are characterized by the following structural units:

R-EP-(CH2)n-Soo-P

where n=0-4 and P represent the corresponding polyvinyl butyral chain.

Watering shall have novotiral according to the invention are distinguished by a clear increase of the mechanical strength as compared with conventional products.

As starting materials can be used all polyvinylbutyral known to the specialist, which is the original polyvinylbutyral in no way limited in molecular weight. However, it is preferable to use polyvinylbutyral with a molecular weight of at least 50000 g/mol. The content of polyvinyl alcohol in polyvinylbutyral used as starting materials is preferably from 10 to 25 wt.% and particularly preferably from 16 to 23 wt.%. The content of polyvinyl acetate in polyvinylbutyral used as starting material, is preferably from 0 to 20 wt.%.

Obtained according to the invention high molecular weight, cross-linked polyvinylbutyral in a preferred form of execution contain a plasticizer or mixture of plasticizers. The plasticizer can be used all known specialist plasticizers, especially esters of polybasic acids, polybasic alcohols or simple oligoesters glycols. The preferred plasticizers are, for example, a complex diesters of aliphatic diols and aliphatic simple polyetherdiols or polyether polyols with aliphatic carboxylic acids, preferably complex diesters polyalkyleneglycol, especially complex diesters of di-, tri - and those who of retranslates with aliphatic (C 6-C10)-carboxylic acids, and the diesters of aliphatic or aromatic (C2-C18)-dicarboxylic acids with aliphatic (C4-C12)-alcohols, preferably vexillationes, as well as mixtures of the mentioned esters. When the plasticizer is used in conventional amounts known to the specialist, the content of the plasticizer is preferably 25-60 weight parts per 100 weight parts of polyvinyl butyral (PVB).

The object of the invention is also a method of obtaining polyvinylbutyral according to the invention, wherein the butyral add a crosslinking agent and, if necessary, a plasticizer mixture, if necessary, homogenize and at a temperature in the range from 80 to 280°With thermally sew.

In a preferred form of execution catalyze crosslinking by adding alkaline or acidic additives.

As alkaline or acidic additives can be used, for example, hydroxides, alkanoate, carboxylates, sulfates, chlorides, nitrates, phosphates of alkaline and/or alkaline earth metals or free organic and/or inorganic acids, and amines.

Obtaining high molecular weight cross-linked polyvinylbutyral according to the invention in a preferred form of execution described below, but which, however, this is not limited.

A crosslinking agent may be added to the butyral, for example, dissolved in the plasticizer, and then the mixture can be homogenized.

The concentration of the crosslinking agent is preferably in the range from 0.01 to 10 wt.%, particularly preferably in the range from 0.1 to 3 wt.%, and, above all, in the region of from 0.1 to 1 wt.% per butyral.

Thermal crosslinking can be carried out in all of the heated aggregates, known to the specialist, such as faucets or autoclaves. However, preferably, the crosslinking is carried out in an extruder, mainly when the temperature of the mass in the region from 80 to 280°C.

The reaction stitching contribute due to the basicity of the polymer, which is typically set for the stabilization of polyvinyl butyral.

The object of this application is also a molding composition containing a high molecular weight crosslinked polyvinyl butyral according to the invention.

Through the above processes extrusion butyral according to the invention using a slit head can also be processed directly in the film. Methods for producing films of polyvinyl butyral quite well-known specialist. Films of high molecular weight cross-linked polyvinylbutyral according to the invention may contain other conventional additives, such as, the example antioxidants, UV stabilizers, dyes, pigments and adhesive grease.

Thus, the object of this application is also a film containing a high molecular weight crosslinked polyvinyl butyral according to the invention.

The films are characterized by high tensile strength, which is particularly advantageous when it receives a triplex, the main area of application of films.

Thus, the next object of this invention is the use of the films according to the invention to obtain a laminated glass.

Hereinafter the invention is described in detail by examples, but is not limited to them.

Measurement methods

The content of polyvinyl alcohol butyral

For this butyral will acetimidoyl excess acetic anhydride in pyridine. After interaction of the excess acetic anhydride, hydrolyzing with water and the resulting product is potentiometrically titrated with sodium hydroxide. The content of polyvinyl alcohol, calculated using consumption of sodium hydroxide.

The content of polyvinyl acetate in the butyral

For this butyral dissolved in a mixture of benzyl alcohol/ethanol. Acetyl group omelet excess alcohol solution of potassium hydroxide. Excess potassium hydroxide is titrated amount of hydrochloric acid. The content is of polyvinyl acetate are calculated according to consumption of hydrochloric acid.

Mw, Mn

Determination of molecular weight of polyvinylbutyral contained in the molding mass is carried out by gel chromatography (GPC) in glacial acetic acid using radiation ionization (RI) detectors. Detector calibration is carried out using reference standards polyvinyl butyral, the absolute values of which are determined by static light scattering.

Alkaline titer polyvinyl butyral

For this butyral dissolved in ethanol and titrated to 0.01 molar hydrochloric acid until the color changes from green to purple. As an indicator of a mixture of methylene blue and neutral red. Alkaline titer calculated by the consumption of hydrochloric acid.

The tensile strength

Before measuring the strength at break of the film was incubated for 24 hours at 23°C and a relative humidity of 50%. The measurement of the strength at break is performed on the machine to study the tensile and compression (manufacturer: Cadis GbR Tour: BRP 201) according to DIN 53455.

The melt index

Film before measurement of the melt index was incubated for 24 hours at 23°C and a relative humidity of 50%. Dimension films is performed on the device for determining the melt index (manufacturer: Göttfert Tour: MP-D) PR is 190° With a load of 2.16 kg using a 2 mm nozzle according to ISO 1133.

The moisture content of the film of polyvinyl butyral

The moisture content of the film of polyvinyl butyral measured in triplex infrared photometer (manufacturer: Pier-Electronic GmbH, Wallau). The measuring device before it is calibrated using appropriate reference standards.

The test shot

The sample for the test shot (Pummel) is made as follows. Film within 24 hours incubated at 23°C and a relative humidity of 30%. Application carried out on 2 mm lightweight glass (Floatglas) F/F - Sn/Sn-orientation film to the surface of the glass. Glass before applying washed completely softened water. The discs manufacturing laminated glass is made by pressing of composite materials in the furnace preform with calender rolls at a temperature of 40-100°With subsequent pressing of triplexes in the autoclave at a pressure of 12 bar and a temperature of 140°C for 30 minutes.

Of laminated glass thus obtained, the test shot cut samples of size 10×30 cm Samples incubated 4 hours at a temperature of -18°C. Then the samples are placed on the base, inclined at an angle of 45°and automatically hit with a hammer to grind glass. The direction of the shock occurs according to figure 1. Assessment is made with what omashu standard scale tests blow from 0 to 10 according to figure 2.

Examples

Comparative example 1

Mixing

370 g of polyvinyl butyral (the content of polyvinyl alcohol=18,9 wt.%, the content of polyvinyl acetate=1.1 wt.%, alkaline titer=16 ml of 0.01 M HCl/100 g) is mixed with 130 g of triethylene glycol bis-2-heptanoate (3G7). Mixing is carried out in a laboratory mixer (manufacturer: Brabender, Modell 826801). The plasticizer before receiving the mixture dissolve 0.75 g Tinvin® P (UV-stabilizer, manufacturer: Ciba Specialty Chemicals). Mixtures of polyvinyl butyral/plasticizer ekstragiruyut flat film with a thickness of 0.8 mm.

Extrusion

The extrusion is carried out on a twin-screw extruder with moving in opposite directions screws (manufacturer: Haake), equipped with a pump to melt slot die, when the temperature of the mass 190°C.

Example 1

Mixing and extrusion occur similarly to comparative example 1. However, in addition to UV-stabilizer, optionally as a cross-linking agent dissolved in the plasticizer still 2,22 g diethyloxalate.

Comparative example 2

Mixing and extrusion occur similarly to comparative example 1. Instead of the polyvinyl butyral used in comparative example 1, using 370 g of polyvinyl butyral content of polyvinyl alcohol is 20.9 wt.%, the content of polyvinyl acetate to 1.1 wt.%, alkaline titer of 16 ml of 0,01M HCl/100 g

Example 2

smeshivanie and extrusion occur similarly to comparative example 1. Instead of the polyvinyl butyral used in comparative example 1, using 370 g of the polyvinyl butyral used in comparative example 2. However, in addition to UV stabilizer as in example 1 optionally as a cross-linking agent dissolved in the plasticizer still 2,22 g diethyloxalate.

Comparative example 3

Mixing and extrusion occur similarly to comparative example 1. However, use 374,5 g of polyvinyl butyral of comparative example 1. Instead of plasticizer (3G7)used in comparative example 1 using output reached 125.5 g disaccrediting (DHA).

Example 3

Mixing is similar to comparative example 3, and the extrusion is carried out similarly to comparative example 1. However, in addition to UV stabilizer as in example 1 optionally as a cross-linking agent dissolved in the plasticizer still 2,22 g diethyloxalate.

Comparative example 4

Mixing

2247 g of polyvinyl butyral (the content of polyvinyl alcohol=20,6 wt.%, the content of polyvinyl acetate=1.1 wt.%, alkaline titer=21 ml of 0.01 M model HC1/100 g) is mixed with 753 disaccrediting. Mixing is carried out in a laboratory mixer (manufacturer: Papenmeier, Tour TGHKV20/KGU63). The plasticizer before receiving the mixture was dissolved 4.5 g Tinvin® P (UV-stabilizer, manufacturer: Ciba Specialty Chemicals). Mixtures of PVB/plasticizer extrude the comfort of a flat film with a thickness of 0.8 mm.

Extrusion

The extrusion is carried out on a twin-screw extruder with moving in the same directions screws (manufacturer: Leistritz)equipped with a pump to melt slot die at a temperature mass 200°C.

Example 4A

Mixing and extrusion occur similarly to comparative example 4. However, in addition to UV-stabilizer, optionally as a cross-linking agent dissolved in the plasticizer still 6,74 g diethyloxalate.

Example 4b

Mixing and extrusion occur similarly to comparative example 4. However, in addition to UV-stabilizer, optionally as a cross-linking agent dissolved in the plasticizer still 5.3g of dimethyloxalate.

Example 4C

Mixing takes place analogously to example 4b and extrusion similarly to comparative example 4. Additionally, prior to mixing with a plasticizer by means of an aqueous solution of potassium hydroxide was adjusted alkaline titer of polyvinyl butyral to 77 ml of 0,01M HCl/100 g

Example 4d

Mixing takes place analogously to example 4C and extrusion is similar to comparative example 4. However, instead of 5.3 g using 10.6 g of dimethyloxalate.

Comparative example 5

Mixing

2220 g of polyvinyl butyral (the content of polyvinyl alcohol=20,6 wt.%, the content of polyvinyl acetate=1.1 wt.%, alkaline titer=21 ml of 0.01 M HCl/100 g) is mixed with 780 g tree jingleball-bis-2-heptanoate. Mixing is carried out in a laboratory mixer (manufacturer: Papenmeier. Tour TGHKV20/KGU63). The plasticizer before receiving the mixture was dissolved 4.5 g Tinvin® P (UV-stabilizer, manufacturer: Ciba Specialty Chemicals). Mixtures of polyvinyl butyral/plasticizer ekstragiruyut flat film with a thickness of 0.8 mm.

Extrusion

The extrusion is carried out on a twin-screw extruder with moving in the same directions screws (manufacturer: Leistritz)equipped with a pump to melt slot die at a temperature mass 200°C.

Example 5

Mixing and extrusion occur similarly to comparative example 5. However, in addition to UV-stabilizer, optionally as a cross-linking agent dissolved in the plasticizer more of 5.24 g of dimethyloxalate.

The examples show that the polyvinyl butyral may be thermally crosslinked derivatives of dicarboxylic acids. Increasing the molecular weight by the action of cross-linking agents has an impact on the increase of molecular weights Mw and Mn, as well as on the decrease of the melt index. The reaction of the crosslinking contributes to increasing alkaline titer used polyvinyl butyral (comparative example 4, example 4b and 4C), as well as increasing the concentration of cross-linking agent (comparative example 4, example 4C and 4d.). The reaction stitching provides improved mechanical properties, laid down is, made from molding masses, has a significant impact on increasing the strength at break. Adhesion of glass to the film by reaction of the stitching remains basically the same, has a noticeable effect on the values of the test shot, which is an important prerequisite for using films in the laminated glass.

1. High molecular weight cross-linked polyvinylbutyral obtained by crosslinking polyvinyl diethyl - and/or dimethyloxalate as a cross-linking agent.

2. Polyvinylbutyral according to claim 1, characterized in that they contain a plasticizer.

3. Polyvinylbutyral according to claim 1 or 2, characterized in that they are suitable for molding masses.

4. Polyvinylbutyral according to claims 1 to 3, characterized in that they are suitable for the production of films.

5. A method of producing polyvinyl one or more of the preceding items, wherein the butyral add a crosslinking agent and, if necessary, a plasticizer mixture, if necessary, homogenize and at a temperature in the range from 80 to 280°With thermally sew.

6. The method according to claim 5, characterized in that the crosslinking catalyze the addition of alkaline or acidic additives.

7. The method according to claim 5 or 6, characterized in that thermal crosslinking is carried out in extrud the re.

8. The film containing the polyvinyl butyral of claim 1 or 2.

9. The film according to claim 8, characterized in that it is suitable for the production of laminated glass.



 

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