Modification of virgin and/or recycled construction polymers, using poly vinyl butyral (PVB), or recycled PVB from industrial waste streams and an alloying copolymer

Abstract

Plasticizer composition for a construction polymers. The plasticizer composition includes 35-65% (by weight) of polyvinylbutyral and 65-35% (by weight) of one or more alloying copolymers. The construction polymer is e.g. polyvinyl chloride, polypropylene, poly urethane, acryl butadiene styrene or polyethylene and/or mixtures thereof. The resulting polymer construction polymer constitutes 25-90% by weight and the plasticizer composition constitutes 10-75% by weight of the polymer blend composition. The components of the plasticizer composition are non-migrating and provide surprising physical properties of the final polymer composition.

Claims

1. A polymer composition comprising a construction polymer and a plasticizer composition, wherein the construction polymer comprises 25-90% by weight and the plasticizer composition comprises 10-75% by weight of the polymer composition; and wherein said plasticizer composition comprises 35-65% (by weight) of polyvinylbutyral (PVB) and 65-35% (by weight) of one or more alloying copolymers, wherein the one or more alloying copolymers includes an Ethylene vinyl alcohol Copolymer Resin.

2. The polymer composition according to claim 1, wherein the polyvinylbutyral component is selected from recycled polyvinylbutyral, virgin polyvinylbutyral, and a mixture thereof.

3. The polymer composition according to claim 1, further comprising one or more other alloying copolymer, wherein the one or more other alloying copolymer is selected from the group comprising: Ethylene copolymer based compatibilizers; a modified ethylene acrylate carbon monoxide terpolymer composition comprising ethylene vinyl acetates (EVAs), polyethylenes, metallocene polyethylenes, ionomers, ethylene propylene rubbers, and polypropylenes; functional polymers working as compatibilization promoter for polar polymers, ethylene vinyl acetate copolymer, and/or mixtures thereof; and a combination thereof.

4. The polymer composition according to claim 1, further comprising one or more other alloying copolymer.

5. The polymer composition according to claim 1, wherein said plasticizer composition comprises 40-60% of PVB with 60-40% by weight of the alloying copolymer(s).

6. The polymer composition according to claim 1, wherein said plasticizer composition comprises 45-55% by weight of PVB and 55-45% by weight of the alloying copolymer(s).

7. The polymer composition according to claim 1, wherein the construction polymer is selected from polyvinyl chloride (PVC), polypropylene (PP), poly urethane (PU), acryl butadiene styrene (ABS), polyethylene (PE), and mixtures thereof.

8. The polymer composition according to claim 1, wherein the plasticizer composition constitutes 30-50% by weight of the polymer composition.

9. The polymer composition according to claim 1, wherein the construction polymer is selected from virgin polyvinyl chloride (PVC), or recycled polyvinyl chloride (PVC), and a mixture thereof.

10. The polymer composition according to claim 1, wherein the polymer composition is mixed with at least one further component.

11. The polymer composition according to claim 10, wherein the at least one further component is selected from a stabilizer, a colorant, an antioxidant, a filler, a UV filter, and a mixture thereof.

12. A method of modifying a construction polymer comprising the steps of: mixing 25-90% by weight of the construction polymer and 10-75% by weight of a plasticizer composition, wherein the plasticizer composition comprises 35-65% (by weight) of polyvinylbutyral (PVB) and 65-35% (by weight) of one or more alloying copolymers, wherein the one or more alloying copolymers includes an Ethylene vinyl alcohol Copolymer Resin; heating the mixed construction polymer and plasticizer composition above a melting point; and shaping the heated mixed construction polymer and plasticizer composition.

13. The method according to claim 12, wherein the heating is included in the shaping.

14. The method according to claim 12, wherein the plasticizer composition comprises 45-55% (by weight) of polyvinylbutyral (PVB) and 55-45% (by weight) of an alloying copolymer.

15. The method according to claim 12, wherein the polymer composition comprises 35-45% by weight of the plasticizer composition and 65-55% by weight of construction polymer.

16. The method according to claim 12, comprising the step of adding at least one additional additive to the mixture of plasticizer composition and construction polymer when the polymer composition is in a solid or melted state.

17. A method for providing a polymer composition, the polymer composition comprising a construction polymer and a plasticizer composition, wherein the construction polymer comprises 25-90% by weight and the plasticizer composition comprises 10-75% by weight of the polymer composition, and wherein the plasticizer composition comprises 35-65% (by weight) of polyvinylbutyral (PVB) and 65-35% (by weight) of at least one alloying copolymer, wherein the at least one alloying copolymer includes an Ethylene vinyl alcohol Copolymer Resin, the method comprising: modifying the construction polymer by mixing 25-90% by weight of the construction polymer and 10-75% by weight of the plasticizer composition, heating the mixed construction polymer and plasticizer composition above a melting point and shaping the heated mixed construction polymer and plasticizer composition.

Description

BRIEF DESCRIPTION

(1) Some of the embodiments will be described in detail, with references to the following Figures, wherein like designations denote like members, wherein:

(2) FIG. 1 depicts average values of flexural modulus for a pure PVC reference specimen and test specimens;

(3) FIG. 2 depicts values of tensile modulus for the pure PVC reference specimen and the test specimens;

(4) FIG. 3 depicts measured hardness for the pure PVC reference specimen and the test specimens;

(5) FIG. 4 depicts measurements of elongation at break for the pure PVC reference specimen and a test specimen;

(6) FIG. 5 depicts measured tensile strength for the pure PVC reference specimen and a test specimen;

(7) FIG. 6 depicts values of flexural modulus for the pure PVC reference specimen and three test specimens;

(8) FIG. 7 depicts values of tensile modulus for the pure PVC reference specimen and the three test specimens of FIG. 6;

(9) FIG. 8 depicts values of Shore D hardness for the pure PVC reference specimen and the three test specimens of FIGS. 6 and 7;

(10) FIG. 9 depicts values of elongation at break for the pure PVC reference specimen and the three test specimens of FIGS. 6-8;

(11) FIG. 10 depicts values of tensile strength for the pure PVC reference specimen and the three test specimens of FIGS. 6-9;

(12) FIG. 11 depicts values of Charpy strength for the pure PVC reference specimen and the three test specimens of FIGS. 6-10;

(13) FIG. 12 depicts values of tensile modulus for the pure PVC reference specimen and three further test samples;

(14) FIG. 13 depicts values of Shore D hardness for the pure PVC reference specimen and the three further test samples of FIG. 12;

(15) FIG. 14 depicts values of elongation at break for the pure PVC reference specimen and the three further test samples of FIGS. 12-13;

(16) FIG. 15 depicts values of Charpy strength for the pure PVC reference specimen and the three further test samples of FIGS. 12-14;

(17) FIG. 16 depicts values of contact angle for the pure PVC reference specimen and two test specimens; and

(18) FIG. 17 depicts values of contact angle for the pure PVC reference specimen and five additional test specimens.

DETAILED DESCRIPTION

(19) Method of modification of Poly vinyl chloride (PVC) and recycled PVC, and other virgin or recycled construction polymers, using poly vinyl butyral (PVB), or recycled PVB from industrial waste streams, as non-migrating plasticizer and impact modifier in a specific and unforeseen combination with alloying polymers as Elvaloy™ (Ethylene Copolymer Resin), Entira™ (Ethylene copolymer based compatibilizer), Fusabond™ (Products line including modified ethylene acrylate carbon monoxide terpolymers, ethylene vinyl acetates (EVAs), polyethylene, metallocene polyethylene, ethylene propylene rubbers and polypropylenes) and Retain™ from Dow (functional polymer working as compatibilization promoter for polar polymers).

(20) PVC and recycled PVC, construction polymers as polypropylene (PP), poly urethane (PU), acryl butadiene styrene (ABS) or polyethylene (PE), can be advantageously modified by use of a pelletized blend of PVB and Elvaloy™ within confined limits. The basis-polymer/PVB/blend with the alloying component chosen from Elvaloy™, Entira™, Fusabond™ and/or Retain™ polymers or copolymers forms uniform, extrudable and moldable polymer alloys with changes in mechanical properties, and a resulting plasticization sterically hindered in migration.

(21) The method may be limited to the following window of formulation for the constituents PVB and alloying copolymer:

(22) 1. PVB: 35-65% by weight mixed with

(23) 2. Alloying copolymer: 65-35% by weight

(24) A formulation may comprise 45-55% by weight of PVB and 55-45% by weight of the alloying copolymer(s). A formulation may comprise 50% by weight of PVB and 50% by weight of the alloying copolymer(s).

(25) This balanced weight ratio of the plasticizer composition relative to the construction polymer leads to an extrudable compound material to be used as part of a construction polymer blend in an amount of 10-75% by weight of the total polymer blend with typical optimal composition having around 40% by weight of plasticizer composition to around 60% by weight of construction polymer(s).

(26) This method can also be used by directly mixing the individual components PVB and the alloying copolymer into the construction polymer or polymers.

(27) PVB, polyvinylbutyral, from automotive front windows are claimed and thoroughly cleaned, sorted and reprocessed to the highest standards. Pellets modified to be compatible with PVC are carefully compounded and extruded as a masterbatch to be blended directly in the PVC-extruding stream.

(28) The confined formulation window ascertains the formation of the microstructures of the blend giving the desired modification of the product and the desired sterically lock of the plasticizer preventing migration, elution or solution of this.

(29) The compound is primarily intended as a totally non-migrating plasticizer for flexible PVC applications and for impact modification of other polymers. Composites and construction polymers can also benefit from this polymer-alloy with both elastic and acoustical properties.

(30) Polymer type: Modified Polyvinylbutyral-alloy in fixed stoichiometric ratio to Ethylene vinyl alcohol Copolymer Resins and/or other alloying copolymers. Due to the alloying of different polymer groups the resulting properties are not linear-combinations of known properties for the pure components, as also the inner microscopical structure are not just a blend of ordinary polymers.

(31) The environmental advantage, of the recovered PVB mined from the direct waste stream to incineration or landfill, has major importance.

(32) PVB acts as a totally nonmigrating plasticizer for PVC and adds valuable properties to the PVC. Further the compound modifies recycled PVC as well, giving possibility to scale and tune properties of rPVC (recycled or reclaimed PVC) for extended and meaningful reuse. In this exists the option to extract unwanted plasticizers from the PVC by liquid CO2 wash in commercially available washing machines, hereby giving possibility of recycling of PVC with a controlled macromolecular plasticizer being an alloyed copolymer.

(33) If PVB is used alone with PVC, there is poor compatibility between both, leading to limited plasticisation effect and brittleness of the resulting polymer. A less successful microstructure may also form giving unwanted drawbacks.

(34) Using embodiments of this invention as solid state non-migrating plasticizer, the effect of PVB can be maximized and the properties of the final polymer matrix enhanced.

(35) Embodiments of the method gives new design possibilities for PVC, since plasticization is scalable, and the microstructure of the blend reproducible and homogeneous.

Regulatory Status

(36) Halogen free, phthalate free compounded alloy specialized to be a modern non-migrating PVC plasticizer with no toxicity and a green profile.

(37) Other additives, such as colorants, preservatives, stabilizers, and/or or antioxidants may be added to the polymer blend. One or more suitable additives may be added in an amount of 0.01-65% by weight relative to the total polymer blend).

(38) Suitable stabilizers for plasticized PVC based polymer blends according to the pre-sent invention are e.g. Calcium-Zinc complexes, stabilisers based on erythritols, e.g. pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate) (marketed as Irganox™ 1010), phosphites, such as Tris(2,4-ditert-butylphenyl)phosphite (marketed as Irgafos™ 168), and/or mixtures thereof.

(39) As example, PVC stabilizers may be added in an amount of e.g. 1% calcium-zinc complex (markted as Baeropan™ MC 8850) and /or 0.4% pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (marketed as Irganox™ 1010) and/or 0.2% Tris(2,4-ditert-butylphenyl)phosphite (marketed as Irgafos™ 168).

(40) Suitable colorants are among others Titanium (IV)-oxide, carbon black, masterbatch and ultrabatch compounded colorants. Also, fillers such as calciumcarbonate, fibers of natural or mineral origin and foaming agents like Hydrocerol® (made by Clairant) can be used.

EXAMPLES

(41) All examples involving test of physical properties made below involves testing at least the same number of test specimens and reference specimens. 4 repetitions are made of each of the examples, unless the relevant standard used for the tests requires otherwise.

(42) Reference sample is pure PVC, (C2H3Cl).sub.n

(43) Melt Temperature 212-260° C.

(44) Tensile Strength 66,1 MPa

(45) Specific Gravity˜1.38-1.45 g/cm.sup.3

(46) Antioxidants have been added to all compositions (1 Baeropan MC 8850 for PVC and 0.4%

(47) Irganox 1010+0.2% Irgafos 168 for Elvaloy 741 and PVB).

(48) Compounds have been prepared on a roll mill at 195° C. for 12 minutes.

(49) Plates have been produced on a Collin press at 180° C. and 150 bars for 3 minutes and then at 50° C. during 5 minutes for cooling.

(50) Physical properties of plasticizer composition with 50%/50% by weight of PVB and an Ethylene Copolymer Resin (Elvaloy 741™, produced by DuPont)

(51) Melting point 130-170° C., extrusion temperature 140-160° C.

Storage Stability

(52) Stored at temperatures between 5° C. and 30° C. Shelf life with full reactivity is 18 months.

(53) Compared to a reference-pure PVC a blend with 40% of 50%/50% compound with Elvaloy 741™ and PVB gives the following results:

Example 1: Preparation of Test Specimens

(54) Processing: Compounds have been prepared on a roll mill at 195° C. for 12 minutes.

(55) Plates have been produced on a Collin press at 180° C. and 150 bars for 3 minutes and then at 50° C. for 5 minutes for cooling. From these plates there has been prepared test samples according to the measures in the ISO and ASTM standards. The test specimens were cut from the plate in the required sizes described in the tests.

Compound Heat Stabilization

(56) Antioxidants have been added to all compositions (1% PVC stabilizer as a Calcium-zinc complex (Baeropan™ MC 8850) and 0.4% PVB stabilizer Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (Irganox™ 1010)+0.2% Tris(2,4-ditert-butylphenyl)phosphite (Irgafos™ 168)

(57) Reference specimens were made from pure PVC.

(58) Test specimens according to the present invention were prepared from a plasticizer blend of 50% by weight of PVB with 50% by weight of Ethylene Copolymer Resin (Elvaloy™ 741) plasticizer composition (named PVB compound in FIGS. 1-17) added in an amount of 40% by weight to 60% by weight of PVC:

Example 2

(59) Flexural modulus measured according to

(60) ISO 178:2010 shows a decrease relative to the PVC of −85% on reference specimens as well as test specimens made according to example 1. Results.

(61) Measurements have been done by testing specimens of rectangular cross-section being 80×10×4 mm, resting on two supports, being deflected by a loading edge acting on the specimen midway between the supports. The test specimen is deflected in this way at a constant rate at midspan until rupture occurs at the outer surface of the specimen or until a maximum strain of 5% is reached, whichever occurs first. During this procedure, the force applied to the specimen and the resulting deflection of the specimen at midspan are measured. The resulting softening/plasticization is interpreted as an evidence of the claimed function of the compound. The results are shown in FIG. 1 where the average values of flexural modulus is shown for the pure PVC reference specimen and the test specimen made with a plasticizer blend of PVB+Elvaloy 741 as explained above.

Example 3

(62) Tensile modulus measured according to ISO 527-2:2012 shows a decrease relative to pure PVC. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A.

(63) The plasticizing of PVC by the plasticizer composition according to the present invention and as discussed in example 1 gives a change of −83%, see FIG. 2.

Example 4

(64) Shore D hardness measured according to the specification in

(65) ASTM D2240-15e1 using a Reichert MHP microhardness tester with a Vickers diamond, and correlation to test samples of known Shore hardness, shows a−27% decrease in hardness, meaning plasticization by the compound has taken place, see FIG. 3.

Example 5

(66) Elongation at break measured according to ISO 527-2:2012 shows an increase relative to PVC of 89%, see FIG. 4. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A in the standard.

(67) The increased ability to stretch is interpreted as an effect of the plasticization effect of the compound.

Example 6

(68) Tensile strength shows relative to PVC a change of −66% see FIG. 5. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A.

(69) The change in tensile strength is interpreted as an effect of the plasticization effect of the compound.

Example 7: Flexural Modulus

(70) A PVC reference specimen is compared to test specimens of polymer blends with 40% rPVB, and to the plasticizer according to the present invention being 50%/50% blend rPVB/Elvaloy 741 (called 1:1 on FIG. 6), and a compound being 75%/25% blend rPVB/Elvaloy 741 (called 3:1 on FIG. 6). (the prefix “r” means that the relevant polymers are recycled from waste fractions of that specific polymer.)

(71) Flexural modulus measured according to ISO 178:2010 shows a decrease relative to the PVC reference specimen, see FIG. 6.

(72) Measurements have been done by testing specimens of rectangular cross-section being 80×10×4 mm, resting on two supports, being deflected by a loading edge acting on the specimen midway between the supports. The test specimen is deflected in this way at a constant rate at midspan until rupture occurs at the outer surface of the specimen or until a maximum strain of 5% is reached, whichever occurs first. During this procedure, the force applied to the specimen and the resulting deflection of the specimen at midspan are measured.

(73) The results show that PVC+40% compound in a 1:1 ratio of PVB and Elvaloy 741® shows a significant lower flexural modulus than if a 3:1 mixing ratio of PVB and Elvaloy 741® was applied, see FIG. 6. Here it must be noted that the pure mix PVB/PVC is resulting in a heterogeneous product with microdomains, with sizes depending on the mixing technique.

Example 8: Tensile Modulus

(74) Tensile modulus is tested on specimens with a composition as described in example 7.

(75) Tensile modulus measured according to ISO 527-2:2012 shows a decrease relative to PVC, see FIG. 7. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A in the standard.

(76) The plasticizing of PVC by the compound claimed shows that PVC+40% compound in a 1:1 ratio of PVB and Elvaloy 741® shows a significantly lower flexural modulus than if a 3:1 mixing ratio was applied. A further increase like 1:2 will give higher tensile modulus.

Example 9: Shore D Hardness

(77) Shore D hardness is tested on specimens with a composition as described in example 7.

(78) Shore D hardness measured according to the specification in ASTM D2240-15e1 using a Reichert MHP microhardness tester with a Vickers diamond shows decrease in hardness, depending on the amount of compound used, see FIG. 8.

Example 10: Elongation of Break

(79) Elongation at break is tested on specimens with a composition as described in example 7.

(80) Elongation of break measured according to ISO 527-2:2012 shows an increase relative to PVC. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A.

(81) The plasticizing of PVC by the plasticizer composition according to embodiments of the present invention shows that PVC+40% compound in a 1:1 ratio shows a significantly higher elongation at break than if a 3:1 mixing ratio was applied. PVB alone with PVC makes a very inelastic product, and the results shows that a certain optimum exists were the values change rapidly, see FIG. 9.

Example 11: Tensile Strength

(82) Tensile strength is tested on specimens with a composition as described in example 7.

(83) Tensile strength measured according to

(84) ISO 527-2:2012 shows a decrease relative to PVC. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A.

(85) The plasticizing of PVC by the compound claimed shows that PVC+40% compound in a 1:1 ratio shows a significantly lower tensile strength than if a 3:1 mixing ratio was applied, see FIG. 10. A further increase like 1:2 will give higher tensile strength.

Example 12: Charpy Test

(86) Charpy strength is tested on specimens with a composition as described in example 7.

(87) Charpy strength is tested according to ISO 148-1:2016 of specimen 55×10×10 mm.

(88) This test consists of breaking a notched test piece with a single blow from a swinging pendulum. The notch in the test piece has a specified geometry and is in the middle between two supports, opposite to the location which is impacted. The energy absorbed in the sample is graphed. Thee result shows a better energy absorption due to energy dissipation in the modified compound, mainly from the PVB molecular backbone, see FIG. 11.

Example 13

(89) Charpy strength is tested on reference specimens of pure PVC and test specimens with a composition of

(90) A: 60% by weight PVC+20% by weight of rPVB and 20% by weight of Elwax™ W40

(91) B: 60% by weight PVC+30% by weight of rPVB and 10% by weight of Elwax™ W40, and

(92) C: 60% by weight PVC+20% by weight of rPVB and 20% by weight of Elvaloy 741

(93) Using as comparable example cheaper Elwax™ W40 the plasticizing effect with rPVB works as well, but the elongation at break suffers, as well as the Charpy strength, see results in FIGS. 12-15:

Example 14: Contact Angle

(94) Contact angle is tested on reference specimens of pure PVC and test specimens with a composition of

(95) A: 60% by weight PVC+40% by weight of rPBV as well as

(96) B: 60% by weight PVC+20% by weight of rPVB and 20% by weight of Elvaloy 741.

(97) Increase of contact angle to water is measured as in ISO 15989:2004. Droplets of double quarts redistilled water is applied with a manual micro syringe equipped with a platinum flat tip needle on top of the specimen. Photographs in 1:1 with LED illumination are image analysed in ImageJ (NIST) making both elliptical and spherical approximation to the drop surface with compensation for gravity. The contact angle is determined on both sides of the image and mediated.

(98) The result shows a slight change in wettability of the surface, where PVB alone adds hygroscopicity and the combination with Elvaloy® rolls this back, see results in FIG. 16.

(99) Contact angle measurements shown in FIG. 17 were tested on reference specimens of pure PVC and different test specimens with varying content of Elvaloy 741 and rPVB (content for each test is mentioned in % by weight of PVC, Elvaloy 741™, rPVB under the bars in the order that they appear in the bars) The contact angle measurements show only slight change in surface wetting with changes in amounts of rPVB and Elvaloy 741.

Example 15: Extraction of PVB

(100) Migration of PVB from test samples is tested on test specimens prepared as described in example 1 with a composition of 60% by weight PVC +20% by weight of rPVB and 20% by weight of Elvaloy 741.

(101) Extraction experiments at 100° C., 30 min, using a 70 ml Duran Soxhlet extractor, and a 10 g sample in double distilled water showed no extraction of the plasticizer of PVB within the measurement accuracy in gravimetry. By Soxhlet extraction at 95° C., 30 min, of a 10 g sample in 98.9% methanol, anhydrous, an insignificant weight loss of 0.01% was measured.

(102) Although the present invention has been disclosed in the form of preferred embodiments and variations thereon, it will be understood that numerous additional modifications and variations could be made thereto without departing from the scope of the invention.

(103) For the sake of clarity, it is to be understood that the use of “a” or “an” throughout this application does not exclude a plurality, and “comprising” does not exclude other steps or elements. The mention of a “unit” or a “module” does not preclude the use of more than one unit or module.