IP Library › Granted Patent US 12,252,606
Granted Patent B2
US 12,252,606 · App. 17/275,274 · Granted Mar 18, 2025

Composites having a thermoplastic matrix

Inventors: Jürgen Franosch (Marl, DE); Andreas Szentivanyi (Essen, DE); Hans Ries (Marl, DE); Horst Beyer (Marl, DE)
Assignee: Evonik Operations GmbH
C08L27/16C08J5/042C08K7/06C09J7/30C09J127/16F16L9/12F16L9/121F16L9/123C08J2327/16C08J2433/14C09J2427/00C09J2433/00
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Quick Facts
Patent No.
US 12,252,606
App. No.
17/275,274
Granted
Mar 18, 2025
Kind
B2
Abstract

The present invention is directed to continuous fiber-reinforced composites having a matrix of modified PVDF. The composite may be a semifinished product or a product or finished part manufactured therefrom. A product according to the invention is pelletized long-fiber material, while a finished part according to the invention is especially a thermoplastic composite pipe.

Claims (63)

1. A composite comprising:

a polymer matrix and

continuous fibers embedded therein,

wherein the polymer matrix has a content of at least 80% by weight of a mixture comprising the following components:

(a) low-viscosity polyvinylidene fluoride (PVDF) as the main component, present in a content of at least 50 parts by weight, and

(b) from 1 to 50 parts by weight of an acrylate copolymer, wherein the acrylate copolymer contains from 1% to 30% by weight of units having carboxylic anhydride units,

wherein the sum total of the parts by weight of a) and b) is 100,

wherein the proportion by volume of the continuous fibers in the composite is from 10% to 80%, and

wherein the low-viscosity polyvinylidene fluoride (PVDF) has a melt flow index of from 18 to 50 g/10 min.

2. The composite according to claim 1 , wherein the PVDF is a homopolymer or a copolymer.

3. The composite according to claim 2 , wherein the composite is a unidirectionally continuous fiber-reinforced tape.

4. The composite according to claim 2 , wherein the composite is a plurality of elongate long-fiber-reinforced pellets having a length of from 4 to 60 mm, produced by cutting the composite in strand form.

5. The composite according to claim 1 , wherein the acrylate copolymer comprises the following units:

(I) from 14% to 80% by weight of ester units of the formula

 with R is methyl, ethyl, propyl or butyl, R 1 is hydrogen or methyl;

(II) from 10% to 75% by weight of imide units of the formula

 wherein R 4 is independently hydrogen or aliphatic or alicyclic radicals having 1 to 8 carbon atoms, and

 R 3 is independently methyl, ethyl, propyl, butyl or phenyl;

 m is 0 or 1;

(III) from 1% to 20% by weight of acid units of the formula

 with R 2 is hydrogen or methyl;

(IV) from 1% to 30% by weight of acid anhydride units of the formula

 with R 5 is independently aliphatic or alicyclic radicals having 1 to 8 carbon atoms;

 n=0 or 1;

where the units (I), (II), (III), and (IV) add up to a total of 100% by weight.

6. The composite according to claim 5 ,

wherein R is methyl,

R 1 is hydrogen, and

R 4 is independently aliphatic or alicyclic radicals having 1 to 4 carbon atoms.

7. The composite according to claim 5 ,

wherein R is methyl,

R 1 is methyl, and

R 4 is hydrogen or methyl.

8. The composite according to claim 5 ,

wherein R is methyl,

R 1 is hydrogen, and

R 4 is hydrogen.

9. The composite according to claim 5 , wherein the composite is a unidirectionally continuous fiber-reinforced tape.

10. The composite according to claim 5 , wherein the composite is a plurality of elongate long-fiber-reinforced pellets having a length of from 4 to 60 mm, produced by cutting the composite in strand form.

11. The composite according to claim 1 , wherein the composite is a unidirectionally continuous fiber-reinforced tape.

12. The composite according to claim 11 , wherein the composite is a plurality of elongate long-fiber-reinforced pellets having a length of from 4 to 60 mm, produced by cutting the composite in strand form.

13. The composite according to claim 1 , wherein the composite is a plurality of elongate long-fiber-reinforced pellets having a length of from 4 to 60 mm, produced by cutting the composite in strand form.

14. An article comprising the composite according to claim 1 , wherein the article is a thermoplastic composite pipe (TCP) comprising the following components from the inside outward:

(I) a tubular liner having one or more layers, the outer surface of which consists of a PVDF molding compound;

(II) a reinforcing ply composed of the composite

(IV) optionally an outer cover ply composed of a polymeric material.

15. The article according to claim 14 , wherein

a design of the TCP is selected from the group consisting of:

(b) liner of a PVDF molding compound/inventive PVDF composite layer/cover ply of a PVDF molding compound;

(e) two-layer liner with an inner layer of a polyamide molding compound and an outer layer of a PVDF/acrylate copolymer blend/inventive PVDF composite layer/layer of a PVDF/acrylate copolymer blend/cover ply of a polyamide molding compound; and

(f) two-layer liner with an inner layer of a polyamide molding compound and an outer layer of a PVDF/acrylate copolymer blend/inventive PVDF composite layer/cover ply of a PVDF molding compound.

16. The article according to claim 15 , wherein the TCP is an umbilical, a riser, a jumper line, a flowline, an intervention line, a downline, an injection line or a pressure line.

17. A process, comprising:

transporting a fluid through the article according to claim 15 ,

wherein the fluid is selected from the group consisting of crude oil, crude gas, triphase, processed oil, processed gas, gasoline, diesel, injection media, and hydraulic oils.

18. The article according to claim 14 , wherein the TCP is an umbilical, a riser, a jumper line, a flowline, an intervention line, a downline, an injection line or a pressure line.

19. A process, comprising:

transporting a fluid through the article according to claim 18 ,

wherein the fluid is selected from the group consisting of crude oil, crude gas, triphase, processed oil, processed gas, gasoline, diesel, injection media, and hydraulic oils.

20. A process, comprising:

transporting a fluid through the article according to claim 14 ,

wherein the fluid is selected from the group consisting of crude oil, crude gas, triphase, processed oil, processed gas, gasoline, diesel, injection media, and hydraulic oils.

21. The composite according to claim 1 , wherein the low-viscosity polyvinylidene fluoride (PVDF) has a melt flow index of from 20 to 45 g/10 min.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 14, 2021
From: FRANOSCH, JÜRGEN; SZENTIVANYI, ANDREAS; RIES, HANS; BEYER, HORST
To: EVONIK OPERATIONS GMBH
Reel/Frame 056847/0304 →
Priority Claims (1)
EP 18195870 · Sep 21, 2018 · regional
Continuity (1)
Related Publication 20220041849A1 · Feb 10, 2022
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