阅读说明：本技术 具有热塑性基材的复合材料 (Composite material with thermoplastic substrate ) 是由 J·弗拉诺斯凯 A·圣伊万伊 H·里斯 H·拜尔 于 2019-09-19 设计创作，主要内容包括：本发明涉及具有改性PVDF基材的连续纤维-增强的复合材料。该复合材料可以是尤其制成的半成品或产品或成品件。根据本发明的产品是粒状长纤维材料,而根据本发明的成品件尤其是热塑性复合材料管。(The present invention relates to a continuous fiber-reinforced composite with a modified PVDF substrate. The composite material may be a semi-finished product or a finished part, in particular made. The product according to the invention is a granulated long fibre material, whereas the finished part according to the invention is in particular a thermoplastic composite pipe.)

1. A composite material consisting of a polymeric matrix and continuous fibers embedded therein, wherein the polymeric matrix consists of at least 80% by weight of a mixture comprising the following components:

a) a low viscosity PVDF as the main component, i.e. at least 50 parts by weight, and

b)1 to 50 parts by weight of an acrylate copolymer, wherein the acrylate copolymer comprises 1 to 30% by weight of units having a carboxylic anhydride unit,

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

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

wherein the percentages of the polymeric matrix and the continuous fibers are based on the total mass or volume of the composite, respectively.

2. Composite material according to claim 1, characterized in that the PVDF is a homopolymer or a copolymer.

3. Composite material according to any one of the preceding claims, characterized in that the acrylate copolymer comprises the following units:

14% to 80% by weight of ester units of the formula:

r is methyl, ethyl, propyl or butyl, R¹Hydrogen or methyl;

II.10 to 75% by weight of imide units of the formula:

R⁴independently is an aliphatic or alicyclic group having 1 to 8 carbon atoms, preferably an aliphatic or alicyclic group having 1 to 4 carbon atoms, more preferably hydrogen or methyl, and

R³independently methyl, ethyl, propyl, butyl or phenyl;

m is 0 or 1;

III.1 to 20% by weight of acid units of the formula:

R²hydrogen or methyl;

IV.1 to 30% by weight of anhydride units of the formula:

R⁵independently an aliphatic or alicyclic group having 1 to 8 carbon atoms;

n is 0 or 1;

wherein the units I, II, III and IV add up to 100% by weight.

4. Composite material according to any of the preceding claims, characterized in that it is a unidirectional continuous fiber-reinforced tape.

5. Elongated long fiber-reinforced pellets having a length of 4 to 60mm prepared by cutting a composite material in strand form according to any of the preceding claims.

6. Thermoplastic composite Tube (TCP) comprising, from the inside outwards:

I. a tubular inner liner having one or more layers, the outer surface of which is composed of a polyamide molding compound or a PVDF molding compound;

a reinforcing layer consisting of a composite material consisting of a polymeric substrate and continuous fibers embedded therein, wherein the polymeric substrate consists of at least 80% by weight of a mixture, wherein said mixture comprises the following components:

a)50 to 99 parts by weight of PVDF, and

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

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

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

wherein the percentages of the polymeric matrix and the continuous fibers are based on the total mass or the total volume of the reinforcement layer, respectively;

optionally further reinforcement layers of the composite consisting of a polyamide substrate and continuous fibers embedded therein, wherein the polyamide substrate consists of at least 80 wt.% of polyamide; and wherein the volume proportion of the continuous fibers in the composite material is additionally from 10 to 80% by weight,

wherein the percentages of polyamide substrate and continuous fibers are based on the total mass or volume of the reinforcement layer, respectively;

an optional outer cover layer comprised of a polymeric material.

7. Thermoplastic composite pipe according to claim 6, characterized in that the design of the TCP is selected from the group:

a) liner of polyamide molding compound/PVDF composite layer of the invention/cover layer of polyamide molding compound;

b) liner of PVDF molding compound/PVDF composite layer of the invention/overlay of PVDF molding compound;

c) liner of PVDF molding compound/cover layer of PVDF composite layer of the invention/polyamide molding compound;

d) liner of polyamide molding compound/PVDF composite layer of the invention/overlay of PVDF molding compound;

e) a two layer innerliner having an inner layer of polyamide molding compound and an outer layer of PVDF/acrylate copolymer blend/a layer of PVDF composite/PVDF/acrylate copolymer blend of the invention/a cover layer of polyamide molding compound;

f) two-layer innerliner with an inner layer of polyamide molding compound and an outer layer of PVDF/propionate copolymer blend/a cover layer of PVDF composite layer/PVDF molding compound of the invention;

g) liner of PVDF or polyamide molding compound/PVDF composite layer of the invention/composite layer with polyamide substrate/cover layer of PVDF or polyamide molding compound.

8. The thermoplastic composite tube according to any one of claims 6 and 7, wherein the TCP is an umbilical, riser, jumper, flowline, interventional tube, downcomer, injection tube or pressure tube.

9. Use of the thermoplastic composite pipe according to any one of claims 6 to 8 for transporting crude oil, crude gas, triphase, processed oil, processed gas, gasoline or diesel, injection media or for conducting hydraulic oil.

Example (b):

in a polymer matrix made from 95% by weight of a low-viscosity homopolymeric PVDF (Solef 1006) mixed with 5% by weight of an acrylate copolymer comprising 10.1% by weight of acid anhydride (IV), 2.9% by weight of acid groups (III), 35% by weight of amide groups (II) and 52% by weight of methacrylate groups (I) without further additives, the tape consists of 45% by volume of carbon fibers (Grafil 34-700D).

After solidification of the eight unidirectional layers of the above adhesive tape to form a semi-finished product (10bar, 240 ℃, 5 minutes holding time), the interlaminar shear strength measured on a flat test specimen according to ASTM D2344-16 was 59 MPa.

Until a predetermined value, no peeling of the substrate and the carbon fiber was observed in the sample; thus, the test states the adhesion of the substrate to the continuous fibers.

For comparison, a semi-finished product was constructed similarly to the working examples, but without the use of the acrylate copolymer. After a comparable setting of the semifinished product, an interlaminar shear strength of 17MPa according to ASTM D2344-16 was found.