Liquid (meth) acrylic syrup it's method of polymerization, use and molded article obtained thereof

Patent metadata

Field	Value
Publication number	US-10040889-B2
Application number	US-201414786193-A
Country	US
Kind code	B2
Filing date	Apr 25, 2014
Priority date	Apr 25, 2013
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

The present invention relates to a liquid (meth)acrylic syrup, its method of polymerization and article obtained thereof. In particular the present invention deals with a liquid (meth)acrylic syrup comprising an initiation system for polymerization at low temperature. More particularly the present invention relates to a liquid (meth)acrylic syrup comprising an initiator system for polymerization at low temperature, said initiating system comprises at least one accelerator, at least one organic aldehyde, at least one peracid and at least one liquid peroxy compound; an impregnation process for a fibrous substrate, the liquid (meth)acrylic syrup for implementing this process, and the obtained impregnated fibrous substrate. The impregnated fibrous substrate is suitable for manufacturing mechanical or structured parts or articles. The present invention concerns also the process for polymerizing a liquid (meth)acrylic syrup comprising an initiation system for polymerization at low temperature said initiating system comprises at least one accelerator, at least one organic aldehyde, at least one peracid, and at least one liquid peroxy compound. The present invention concerns also manufacturing process for manufacturing mechanical or structured parts or articles and three-dimensional mechanical or structured parts obtained by this process.

First claim

The invention claimed is:

1. Liquid (meth) acrylic syrup comprising:
a) a (meth)acrylic polymer,
b) a (meth)acrylic monomer,
c) at least one initiating system for starting the polymerization of the (meth) acrylic monomer,
wherein said initiating system comprises
from 0.1 to 5 part by weight of peroxy compound,
≤1 parts by weight of accelerator calculated on the part of the transition metal in the accelerator,
from 1 to 10 parts by weight of at least one organic aldehyde, and
from 1 to 10 parts by weight of at least one organic peracid in view of the sum of the (meth)acrylic monomer and a (meth)acrylic polymer, the two together make up 100 parts by weight,
wherein the peroxy compound is a liquid at a temperature between 0° C. and 50° C.

2. The liquid (meth) acrylic syrup according to claim 1 comprising:
a) from 10 to 60 part by weight of (meth)acrylic polymer,
b) from 40 to 90 parts by weight of (meth)acrylic monomer,
c) from 2.1 to 26 parts by weight of one initiating system for starting the polymerization of the (meth) acrylic monomer.

3. The liquid (meth) acrylic syrup according to claim 1 , wherein the accelerator comprises a transition metal compound.

4. The liquid (meth) acrylic syrup according to claim 3 wherein the transition metal is chosen from the 4 th period.

5. The liquid (meth) acrylic syrup according to claim 3 wherein the transition metal is chosen from manganese, cobalt, iron or copper and or mixtures thereof.

6. The liquid (meth) acrylic syrup according to claim 1 wherein the peroxy compound is an organic peroxide comprising from 2 to 30 carbon atoms.

7. The liquid (meth) acrylic syrup according to claim 1 wherein the organic aldehyde has the general formula R1CHO, wherein R1 is an organic group comprising between 1 and 30 carbon atoms.

8. The liquid (meth) acrylic syrup according to claim 1 wherein the organic peracid has the general formula R1COOOH, wherein R1 is an organic group comprising between 1 and 30 carbon atoms.

9. The liquid (meth) acrylic syrup according to claim 1 , wherein said liquid (meth)acrylic syrup has a dynamic viscosity of a value in the range from 10 mPa*s to 10000 mPa*s, measured at 25° C.

10. A process for polymerizing a liquid (meth) acrylic syrup comprising the step of
mixing the components of said liquid (meth)acrylic syrup at a time of less than 30 minutes before injection in a mold or impregnation of a fibrous substrate, wherein said components of said (meth)acrylic syrup comprise:
a) a (meth)acrylic polymer,
b) a (meth)acrylic monomer,
c) at least one initiating system for starting the polymerization of the (meth) acrylic monomer,
said initiating system comprises from 0.1 to 5 part by weight of peroxy compound,
≤1 parts by weight of accelerator calculated on the part of the transition metal in the accelerator,
from 1 to 10 parts by weight of at least one organic aldehyde, and
from 1 to 10 parts by weight of at least one organic peracid

in view of the sum of the (meth)acrylic monomer and a (meth)acrylic polymer, the two together make up 100 parts by weight,
wherein the peroxy compound is a liquid at a temperature between 0° C. and 50° C.

11. The process according to claim 10 , wherein said liquid (meth) acrylic syrup comprises:
a) from 10 to 60 part by weight of (meth)acrylic polymer,
b) from 40 to 90 parts by weight of (meth)acrylic monomer,
c) from 2.1 to 26 parts by weight of one initiating system for starting the polymerization of the (meth) acrylic monomer.

12. An impregnation process for impregnating a fibrous substrate, wherein said fibrous substrate is made of long fibres said long fibers having an aspect ratio of at least 1000, and said process comprises a step of impregnating said fibrous substrate with a liquid (meth) acrylic syrup comprising:
a) a (meth)acrylic polymer,
b) a (meth)acrylic monomer,
c) at least one initiating system for starting the polymerization of the (meth) acrylic monomer,
wherein said initiating system comprises from 0.1 to 5 part by weight of peroxy compound,
≤1 parts by weight of accelerator calculated on the part of the transition metal in the accelerator,
from 1 to 10 parts by weight of at least one organic aldehyde, and
from 1 to 10 parts by weight of at least one organic peracid
in view of the sum of the (meth)acrylic monomer and a (meth)acrylic polymer, the two together make up 100 parts by weight,
wherein the peroxy compound is a liquid at a temperature between 0° C. and 50° C.

13. The impregnation process according to claim 12 , wherein said liquid (meth)acrylic syrup has a dynamic viscosity of a value in the range from 10 mPa*s to 10000 mPa*s, measured at 25° C.

14. The impregnation process according to claim 12 , wherein the (meth)acrylic polymer is a homo- or copolymer of methyl methacrylate (MMA) or a mixture thereof.

15. The impregnation process according to claim 12 , wherein the copolymer of methyl methacrylate (MMA) comprises from 70% to 99.7% by weight of at least one monomer having at least one ethylenic unsaturation that can copolymerize with methyl methacrylate.

16. A manufacturing process for manufacturing mechanical or structured parts or articles comprising following steps:
a) impregnating a fibrous substrate with a liquid (meth) acrylic syrup according to claim 1 ,
b) polymerising the liquid (meth) acrylic syrup impregnating said fibrous substrate.

17. The process according to claim 16 , wherein the impregnation of the fibrous substrate in step a) is made in a closed mold.

18. The process according to claim 16 wherein step a) and step b) occur in the same closed mold.

19. The process according to claim 16 wherein the process is resin transfer molding or infusion.

20. The process according to claim 16 , wherein the temperature of the polymerization is step b) is below 40° C.

21. Three-dimensional mechanical or structured parts obtained by the manufacturing process according to claim 16 .

22. Part according to claim 21 , which is a automobile part, boat part, train part, sport article, plane or helicopter part, space ship or rocket part, photovoltaic module part, wind turbine part, furniture part, construction or building part, telephone or cell phone part, computer or television part, printer and photocopy part.

Assignees

• Arkema France

Inventors

• Gerard Pierre
• Callin Daniel

Classifications

• C08J2351/00

  Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers · CPC title

• C08F265/06 Primary

  Polymerisation of acrylate or methacrylate esters on to polymers thereof · CPC title

• B29C70/42

  for producing articles of definite length, i.e. discrete articles · CPC title

• C08J2333/06

  of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical · CPC title

• C08J5/24

  Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs · CPC title