阅读说明：本技术 拉挤成型件、其制造和用途 (Pultruded part, production and use thereof ) 是由 D.韦格纳 H.拉泽尔恩贝格 A.霍夫曼 H.施密特 R.德尔霍芬 于 2018-04-17 设计创作，主要内容包括：本发明涉及基于聚氨酯和碳纤维的拉挤成型件、其制造和用途。(The invention relates to pultrudes based on polyurethane and carbon fibres, the production and use thereof.)

1. Polyurethane pultrusion from 40-80 vol.% carbon fiber and polyurethane resin having a density > 1.05g/cm high, wherein the polyurethane may be prepared from

A polyisocyanate component (A),

A polyol component (B) consisting of

b1) A mixture of at least two polyols,

b2) From 0 to 20% by weight, based on the total weight of (B), of one or more other isocyanate-reactive compounds other than B1),

forming a reaction mixture in

b3) From 0 to 5% by weight, based on the total weight of (B), of one or more catalysts,

b4) From 0 to 20% by weight, based on the total weight of (B), of further auxiliaries and/or additives,

0.1 to 8 wt.%, based on the total weight of (B), of at least one internal mold release agent (C),

In the presence of a catalyst to obtain,

it is characterized in that

polyisocyanate component (A)

1) containing > 55% by weight, based on the total weight of (A), of monomeric diphenylmethane diisocyanate (MDI), wherein

2) the sum of 2,2'-MDI and 2,4' -MDI being < 40% by weight, based on the total weight of (A), and

3) The prepolymer is not contained in the mixture, and the prepolymer,

The polyol component (B) is free of polymer polyols,

(B) The number average hydroxyl value of the total of the components is more than or equal to 400 mg KOH/g and less than or equal to 2000 mg KOH/g, and

(B) Has a number average of from 2.5 to 3.5, and

(A) The ratio of the number of NCO groups in (A) to the sum of the number of OH groups in (B) and (C), multiplied by 100, has a value of from 90 to 120.

2. Polyurethane pultrusion formed from 50-75% by volume of carbon fibers and polyurethane resin with a density of > 1.05g/cm 3, wherein the polyurethane can be formed from

A polyisocyanate component (A),

A polyol component (B) consisting of

b1) A mixture of at least two polyether polyols,

b2) 0 to 15% by weight, based on the total weight of (B), of an aliphatic alcohol,

Forming a reaction mixture in

b3) 0 to 5% by weight, based on the total weight of (B), of one or more metal catalysts,

b4) From 0 to 20% by weight, based on the total weight of (B), of further auxiliaries and/or additives,

0.1 to 6% by weight, based on the total weight of (B), of at least one internal mold release agent (C),

In the presence of a catalyst to obtain,

It is characterized in that

Polyisocyanate component (A)

1) Containing > 65% by weight, based on the total weight of (A), of monomeric MDI, where

2) the sum of 2,2'-MDI and 2,4' -MDI being less than or equal to 30% by weight, based on the total weight of (A), and

3) The prepolymer is not contained in the mixture, and the prepolymer,

The polyol component (B) is free of polymer polyols,

(B) The number average hydroxyl value of the total of the components is more than or equal to 420 mg KOH/g and less than or equal to 700 mg KOH/g, and

(B) Has a number average value of 2.6 to 2.8, and

(A) The ratio of the number of NCO groups in (A) to the sum of the number of OH groups in (B) and (C), multiplied by 100, has a value of from 90 to 120.

3. A method of manufacturing a polyurethane pultrusion as claimed in claim 1 or 2, which comprises the steps of:

i) mixing components (A), (B) and (C) to obtain a polyurethane reactive mixture,

ii) conveying the polyurethane reactive mixture to an injection tank,

iii) simultaneously with process step ii), introducing the carbon fibers through an injection box to impregnate the carbon fibers with the polyurethane reactive mixture,

iv) introducing carbon fibres impregnated with the polyurethane reactive mixture into a heated curing mould,

v) curing the carbon fibres impregnated with the polyurethane reactive mixture in a curing mould to form a polyurethane pultrusion,

vi) pulling the cured polyurethane pultrusion from the curing die by means of a pulling mechanism,

vii) cutting the cured polyurethane pultrusion to the desired length.

4. use of the polyurethane pultrusion as claimed in claim 1 or 2 as lightweight reinforcing profiles and structural elements in vehicle construction and aircraft construction and in wind power stations.

Example (b):

The viscosity distribution of the polyurethane reactive mixtures according to the invention was determined using a rheometer after mixing components (a), (B) and (C) and compared with polyurethane reactive mixtures not according to the invention.

Rheometer MCR 502 from Anton Paar

The viscosity measurement is carried out in accordance with DIN 53019-1:2008-09 (H < < R), (d/dt = 1001/s): d/dt = shear rate, plate-plate measuring system PP 25, rotation measurement

to record the viscosity distribution, the internal mold release agents were added in the amounts indicated in each case to the polyol mixtures listed in Table 1, stirred vigorously with one another, and tempered to 23 ℃. Subsequently, an amount of isocyanate tempered to 23 ℃ and corresponding to the index shown in table 1 was added and the mixture was stirred for 20 seconds. Then 300 microliters of the mixture was immediately placed on the plate of the rheometer and the measurement was started. The rheometer plates were tempered to 23 ℃ before the measurement started. The plate temperature was heated to 139 ℃ at the beginning of the measurement at a rate of 33K/min and the viscosity minima after different time intervals were determined. Here, the first measurement point is recorded 15 seconds after the end of mixing the polyol/mold release mixture with the isocyanate.

Fiber impregnation and curing of the polyurethane reactive mixture was also evaluated during the manufacture of polyurethane pultrudates.

A pultrusion apparatus having a heatable die with an internal dimension of 60 x 5 mm and an injection box mounted upstream of the die was used. Accordingly, rectangular profiles with a width of 60 mm and a wall thickness of 5 mm were produced. Carbon fiber rovings (Pyrofil TRW 4050L KNA from Mitsubishi Rayon Co. Ltd.) were used as reinforcement material and pulled through injection boxes and molds. The carbon fiber concentration in the finished profile was about 65% by volume. The indicated amounts of internal mold release agents were added in each case to the polyol mixtures listed in table 1 and stirred vigorously. These mixtures were mixed in each case with so much isocyanate at 23 ℃ using a low-pressure mixer with a static mixer that the respective NCO indices shown in table 1 were present and the resulting polyurethane reactive mixtures were continuously injected into an injection box. The wetted carbon fibers were continuously pulled through the heated die at a speed of 1.50 m/min and cured by the output mechanism of the pultrusion apparatus. The tempering of the mold was divided into 3 zones, where the temperature in zone 1 was 170 ℃ (mold entrance in the output direction), 190 ℃ (mold center) in zone 2, and 200 ℃ (mold exit) in zone 3. The finished profile is then continuously cut to the desired length.

The following raw materials were used:

Polyol 1 glycerol-initiated triol, propoxylated, OHZ (hydroxyl number) = 235 mg KOH/g

Polyol 2 glycerol-initiated triol, propoxylated, OHZ = 1050 mg KOH/g

Polyol 3 glycerol-initiated triol, propoxylated, OHZ = 400 mg KOH/g

Polyol 4 propylene glycol initiated diol, propoxylated, OHZ = 28 mg KOH/g

Polyol 5 propylene glycol initiated diol, propoxylated, OHZ = 515 mg KOH/g

Polyol 6 propylene glycol initiated diol, propoxylated and ethoxylated, OHZ = 57 mg KOH/g

polyol 7 glycerol-initiated triol, propoxylated, OHZ = 800 mg KOH/g

Glycerol

Catalyst 1:2, 2' - [ (dioctylstannylene) bis (thio) ] diacetic acid diisooctyl ester

Catalyst 2 Toyocat-DB30 from Tosoh Corporation

Water adhesive 1: MOLSIV L-powder of UOP company

Water adhesive 2, rather than MOLSIV L-paste (50% dispersion of MOLSIV L powder in castor oil) of UOP company

higher functional acid based on ester of phthalic acid with diethylene glycol, acid number = 127 mg KOH/g

Internal mold Release 1 Luvotident TL HB 550 from Lehmann & Voss for pultrusion

Internal MOLD Release 2 MOLD WIZ INT-1947 MCH

MDI 1, polymeric MDI having an NCO content of 32.0% by weight, a monomeric MDI content of 69% by weight; the total content of 2,4'-MDI and 2,2' -MDI amounting to 8% by weight

MDI 2, polymeric MDI having an NCO content of 31.5% by weight, a monomeric MDI content of 47.5% by weight; the total content of 2,4'-MDI and 2,2' -MDI was 5.4% by weight

MDI 3, monomeric MDI having an NCO content of 33.6% by weight; the total content of 2,4'-MDI and 2,2' -MDI was 55.1% by weight

MDI 4: 80 GT (parts by weight) of polymeric MDI having a viscosity of 200 mPas at 25 ℃ and a monomeric MDI content of 39% by weight and 20 GT of a mixture of monomeric MDI based on 2,4'-MDI and 4,4' -MDI. The content of the mixture of monomeric MDI was 51.2% by weight.