(Meth)acrylic polymer composition its method of preparation and use

Patent metadata

Field	Value
Publication number	US-11840625-B2
Application number	US-201816955167-A
Country	US
Kind code	B2
Filing date	Dec 18, 2018
Priority date	Dec 18, 2017
Publication date	Dec 12, 2023
Grant date	Dec 12, 2023

Abstract

The present invention relates to a (meth)acrylic polymer composition. In particular the present invention it relates to polymeric composition suitable for security glazing. The invention also relates to a process for manufacturing such a polymeric composition suitable for security glazing. More particularly the present invention relates to a bullet resistant (meth)acrylic polymer composition and relates also to a process for preparing such a bullet resistant (meth)acrylic polymer composition and its use in glazing.

First claim

The invention claimed is:

1. A polymeric composition suitable for bullet resistant applications comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature of greater than 0° C. and of elastomeric domains having a characteristic dimension of less than 100 nm consisting of macromolecular sequences (II) having a flexible nature with a glass transition temperature of less than 0° C., wherein the macromolecular sequences (II) having a flexible nature have a weight average molecular weight Mw of between 150,000 and 800,000 g/mol; and wherein the crosslinked (meth)acrylic composition comprises 4%-10% of a crosslinking agent by weight of the crosslinked (meth)acrylic composition;
wherein polydispersity index PI of the macromolecular sequences (II) having a flexible nature is between 3.0 and 6.0.

2. The polymeric composition according to claim 1 , wherein the weight average molecular weight Mw of the macromolecular sequences (II) having a flexible nature is between 225,000 and 600,000 g/mol.

3. The polymeric composition according to claim 1 , wherein the weight average molecular weight Mw of the macromolecular sequences (II) having a flexible nature is between 240,000 g/mol and 600,000 g/mol.

4. The polymeric composition according to claim 1 , wherein the weight average molecular weight Mw of the macromolecular sequences (II) having a flexible nature is between 255,000 g/mol and 600,000 g/mol.

5. The polymeric composition according to claim 1 wherein the content of crosslinking agent is between 4% and 8% by weight, with respect to the crosslinked (meth)acrylic composition.

6. The polymeric composition according to claim 1 , wherein the content of crosslinking agent is between 4% and 5% by weight, with respect to the crosslinked (meth)acrylic composition.

7. The polymeric composition according to claim 1 , wherein the macromolecular sequences (II) in the polymeric composition is between 1 wt % and 30 wt %, with respect to the polymeric composition comprising crosslinked (meth)acrylic composition and macromolecular sequences (II).

8. The polymeric composition according to claim 1 , wherein the matrix (I) comprises from 51 wt % to 100 wt %, of methyl methacrylate monomer units.

9. The polymeric composition according to claim 1 , wherein the matrix (I) comprises from 90 wt % to 100 wt % of methyl methacrylate monomer units.

10. The polymeric composition according to claim 1 , wherein the macromolecular sequences (II) are prepared from one or more monomer(s) Mo2 chosen from:
acrylic monomers of formula CH 2 ═CH—C(═O)—O—R 1 , where R 1 denotes a hydrogen atom or a linear, cyclic or branched C 1 -C 40 alkyl group optionally substituted by a halogen atom, or a hydroxyl, alkoxy, cyano, amino, or epoxy group;
methacrylic monomers of formula CH 2 ═C(CH 3 )—C(═O)—O═R 2 , where R 2 denotes a hydrogen atom, or a linear, cyclic, or branched C 1 -C 40 alkyl group optionally substituted by a halogen atom, or a hydroxyl, alkoxy, cyano, aminoor epoxy group; and
vinylaromatic monomers.

11. The polymeric composition according to claim 1 , wherein the composition possesses a swelling index of less than 200% in acetone at 20° C.

12. The polymeric composition according to claim 1 , wherein the composition is in form of a sheet or a cast sheet.

13. The polymeric composition according to claim 1 , wherein said composition is part of a multilayer composition.

14. A process for manufacturing the polymeric composition according to claim 1 comprising the steps of:
a) preparing the macromolecular sequences (II)
b) mixing the macromolecular sequences (II) of step a) with methyl methacrylate, and optionally the crosslinking agent, optionally at least one comonomer M01 and optionally at least one radical initiator;
c) mixing the composition comprising the macromolecular sequences (II) and methyl methacrylate with 4% to 10% of the crosslinking agent by weight of the methylmethacrylate, optionally the comonomer M01 if comonomer M01 was not added in step b), and optionally the at least one radical initiator, if the at least one radical initiator has not been added in step b);
d) casting the mixture obtained in step c) in a mold and then heating the mixture according to a temperature cycle in order to obtain a cast sheet.

15. The process according to claim 14 , wherein step a) comprises: preparing the macromolecular sequences (II) by mixing monomer(s) intended to form the macromolecular sequences (II), with an alkoxyamine of general formula Z(-T) n , n which Z denotes a polyvalent group, T denotes a nitroxide and n is an integer greater than or equal to 1.

16. A process for manufacturing the polymeric composition according to claim 1 , comprising the following steps:
a) preparing the macromolecular sequences (II);
b1) mixing the macromolecular sequences (II) of step a) with methylmethacrylate;
b2) partly polymerizing the macromolecular sequences (II) and methyl methacrylate obtained in step b1) and optionally adding additional methyl methacrylate;
c) mixing the partly polymerized composition obtained in step b2) with crosslinking agent, optionally at least one comonomer M01, and at least one radical initiator.

17. A process for manufacturing a polymeric composition according to claim 1 , comprising the following steps:
a1) preparing an alkoxyamine of general formula Z(-T) n , in which Z denotes a polyvalent group, T denotes a nitroxide and n is an integer greater than or equal to1;
a2) preparing the macromolecular sequences (II) by mixing monomer(s) intended to form the macromolecular sequences (II) with the alkoxyamine of step a1);
b1) mixing the macromolecular sequences (II) of step a2) with methyl methacrylate;
b2) partly polymerizing the macromolecular sequences (II) and methyl methacrylate and optionally adding optionally additional methyl methacrylate;
c) mixing the partly polymerized composition obtained in step b2) with crosslinking agent, optionally at least one comonomer M01, and at least one radical initiator;
d) casting the mixture obtained in step c) in a mold and then heating the mixture according to a temperature cycle in order to obtain a cast sheet.

18. The process according to claim 15 , wherein the alkoxyamine has the following formula:

19. A bullet resistant material comprising the polymeric composition according to claim 1 .

20. The bullet resistant material of claim 19 , wherein said bullet resistant material is an observation slots, viewing openings, personal protection equipment, or security glazing.

21. The polymeric composition according to claim 10 , wherein the one or more monomer(s) Mo2 comprise at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, hydroxyalkyl methacrylates, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2- ethyl-hexyl acrylate, glycidyl acrylate, hydroxyalkyl acrylates, or acrylonitrile.

Assignees

• Trinseo Europe Gmbh

Inventors

• Boutillier Jean-Marc
• Carrere Veronique L
• Pery Stephanie
• Cazaumayou Sylvie
• Bourrigaud Sylvain

Classifications

• C08L33/12 Primary

  Homopolymers or copolymers of methyl methacrylate · CPC title

• B32B17/10

  of synthetic resin · CPC title

• B32B27/08

  of synthetic resin · CPC title

• B32B27/308

  comprising acrylic (co)polymers · CPC title

• C08F220/1804

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title