# Patent

## Title
Phenolic resin systems for fiber reinforced composite manufacture

## Abstract

The invention includes formulations useful for creating reinforced composites based on 1) novolac resin compositions, and, 2) non-formaldehyde hardeners, as well as processes for manufacturing components using said reinforced composites.

## Background
This application is a continuation-in-part of U.S. patent application Ser. No. 10/830,808 filed Apr. 23, 2004 now allowed, which is a continuation-in-part of U.S. patent application Ser. No. 10/383,272 filed Mar. 7, 2003 abandoned.


BACKGROUND OF INVENTION
1. Field of the Invention
The invention is directed toward phenolic resin compositions which are useful in the manufacture of reinforced composites.
2. Description of the Prior Art
Phenolic resins can be broadly divided into two general classes: novolacs and resoles. Novolac resins are generally characterized as being formaldehyde deficient. That is to say that the ratio of formaldehyde to phenolic groups is <1. Resole resins are generally characterized as being formaldehyde rich. That is to say that the ratio of formaldehyde to phenolic groups is >1. Both novolacs and resoles may incorporate a variety of phenolic compounds, alone or in combination, including but not limited to phenol, resorcinol, bisphenols, phloroglucinol, cresols, alkyl phenols, phenyl ethers, tannins, and lignins. Similarly, other aldehydes may be substituted in whole or in part for formaldehyde, including but not limited to acetaldehyde, propionaldehyde, cyclohexanedicarboxaldehydes, benzaldehydes, furfural, and other aryl or heterocyclic aldehydes.
Novolac resins are usually cured (crosslinked, hardened) through the use of formaldehyde, formaldehyde-donating hardener compounds, or formaldehyde equivalent compounds. Hexa-methylenetetramine (hexa) and paraformaldehyde are often used commercially to cure novolac resins. In addition to a source of formaldehyde, heating and the presence of a catalyst are usually employed to accelerate the rate and extent of curing. Catalysts may include inorganic bases such as sodium or potassium hydroxide, Lewis acids such as zinc chloride or zinc acetate, or amines such as triethylamine.
The ideal phenolic resin for composite applications such as pultrusion, filament winding or vacuum assisted resin transfer would possess a number of key attributes:

    
    
        it would be capable of being formulated to give a liquid resin at ambient or near ambient temperature using little or no inert solvents;
        it would have a low free phenolic monomer content;
        it would be able to utilize processing equipment made with standard materials of construction;
        it would be curable through reaction with hardeners.
    
    


Depending upon their molecular weight, resole resins can be either solids or liquids. They are cured by heating either alone or, more typically, in the presence of an acid catalyst. Composite applications are currently dominated by liquid resole resin formulations almost to the exclusion of novolacs. Yet, resoles do not possess the ideal solution because their acid catalysts require the use of processing equipment made from costly, acid-resistant materials. Furthermore, the acid catalysts necessary for curing severely limit their processing window (pot life) and storage stability. Another drawback of resoles is their relatively high solvent content needed to keep the formulation viscosity within acceptable processing parameters.
Novolac resins are typically solids that require heating in the presence of a hardener (formaldehyde source or equivalent) in order to cure to a crosslinked resin. These products are ideally suited for molding applications where the resins are compounded (blended) with hardeners, fillers, and reinforcements. However, there are certain applications, such as adhesives and composites, where it is more advantageous to use a liquid resin system. Liquid novolac resins are most often obtained in one of three ways:

    
    
        by mixing the solid resins with aqueous base;
        by dissolving the resin in an organic solvent;
        by employing a large excess of phenolic monomer to act as a reactive diluent.
    
    


While the water or organic solvent based formulations may be suitable for adhesive applications or for the preparation of certain prepregs, they are not desirable for composite applications where the trapped solvents lead to the generation of voids. Offgassing of solvents is not the issue with formulations containing excess phenolic monomers. Rather, the large excess of free monomers may result in undesirably long curing times or worker exposure issues.
The potential usefulness of phenolic-based fiber reinforced composites has long been recognized. The excellent flame, smoke and toxicity (FST) properties of phenolics in fire situations have made them the material of choice in the construction of aircraft interiors, rail coaches and other areas with high concentrations of people with limited egress routes. Unfortunately, phenolic polymers and their composite systems are also well known to be difficult to process and the final parts brittle.
Dailey, in two closely related U.S. Pat. Nos. 5,075,413 and 5,075,414, discusses the need for phenolic resin systems with improved processing capabilities. Specifically, he discloses the use of mixtures of phenolic resoles with resorcinol-based novolacs to provide a low temperature cure system while retaining the excellent FST properties of phenolics. He additionally discusses the use of liquid methylene donors to partially dissolve paraformaldehyde thereby reducing the overall solvent content of the resin formulations. This was anticipated to provide enhanced physical properties of the final composite parts through reduced void content.
Shea also has several patents relating to fire resistant phenolic resin compositions for use in composites. In U.S. Pat. No. 4,053,447, he discusses the use of mixtures of aldehydes with paraformaldehyde to cure resorcinol-based novolac resins. The aldehydes were said to give improved resistance to cracking and embrittlement without sacrificing FST properties. In U.S. Pat. No. 4,107,127, he discloses the use of paraformaldehyde with aqueous formaldehyde to cure resorcinol based novolac resins with improved embrittlement properties without sacrificing FST properties. Shea patents U.S. Pat. No. 4076873, EP0368927, WO 89/01013 and U.S. Pat. No. 5,202,189 are similar to the aforementioned Shea art in that they discuss resorcinol-based novolacs cured with mixtures of formaldehyde(s) and other aldehydes. In US patent application 2004/0036056, he specifically discusses the use of a four part, non-formaldehyde-containing hardener for phenolic resin systems useful for composites. His hardener consists of a non-formaldehyde methylene donor, a pH adjuster, a viscosity adjuster and a polymerization shortstop to retard the polymerization. He also claims a small amount of water in the hardener system is required for proper cure to be obtained.
SUMMARY OF INVENTION
Novolac resins can be cured using standard hardeners such as hexa, paraformaldehyde, or formaldehyde in aqueous or organic solvent solutions. However, it is envisioned within the scope of this invention that the preferred hardeners be chosen from among several classes of novel hardeners including oxazolidines, nitroalcohols, hydroxylamines, aminonitroalcohols, nitroamines, nitroolefins, nitroacetals, nitrones, amines, imines, halonitroparaffins, oxazines, azaadamantanes, hexamethylenetetramine salts, imidazolidines, triazines, nitrooxazolidines, imidazolidine-oxazolidine hybrids and hexahydropyrimidines used either alone or in various combinations with each other and/or with hexa or paraformaldehyde. The hardener systems are the subject of co-pending U.S. patent application Ser. Nos. 10/830,808 and 10/383,272, the disclosures of which are incorporated herein by reference. The hardeners are effective in curing a wide range of phenolic novolac resins. Through the judicious selection of these hardeners, used either alone or in various combinations, it is possible to advantageously vary the processing parameters of these phenolic resin systems. Higher curing rates, reduced volatiles emission and reduced post-cure cycles are advantageous improvements as compared to standard hexa-cured systems. These process improvements and reduction in cycle time have obvious economic benefits.
The resin systems described in this invention can be applied in any application where phenolic resins are used, including but not limited to adhesives, molding compounds, foundry materials, abrasives, friction materials, insulation, laminates, coatings, prepregs, electronics, fire resistant, and flame-retardant end uses. These liquid novolac formulations are well suited for pultrusion, filament winding, and vacuum assisted resin transfer composite applications. In particular, we have developed formulations that are ideally formulated for pultrusion and filament winding. The formulations, pultrusion processing, filament winding processing and final composite parts are all within the scope of this invention.


DETAILED DESCRIPTION OF INVENTION
The invention includes formulations useful for creating reinforced composites based on 1) novolac resin compositions, and, 2) non-formaldehyde hardeners. These formulations are liquids, moderate in viscosity and suited for use in composite manufacturing. Additionally, the process for curing these formulations in the presence of reinforcements and the resulting cured plastics are also covered. The novolac resins may be based on combinations of aromatic monomers and such resins are described in the examples of this patent. Additionally, the resin systems may or may not include solvents and vary in pH depending on their method of preparation. For this invention, the resins are used as a solution in reactive diluent or solvent with a pH ranging from 8-12. Examples of reactive diluents are phenol, substituted phenols, aliphatic aldehydes other than formaldehyde, furfural or furfuryl alcohol, and low molecular weight phenolic resole resins. Examples of solvents include methanol, ethanol, higher alcohols, benzyl alcohol, glycols, glycol ethers, esters, water, and other typical low cost organic solvents that will solvate the novolac resin.
The curing agents, i.e., hardeners and catalysts, may be drawn from a wide variety of existing and new oxazolidines, nitroalcohols, nitroacetals, nitroolefins, nitroamines, aminonitro-alcohols, hexahydropyrimidines, nitrones, hydroxylamines, imines, oxazines, triazaadamantanes, hexa salts, and halogenated derivatives of these compounds. These are described fully in U.S. patent application Ser. No. 10/830,808 and co-pending U.S. patent application Ser. No. 10/383,272, the disclosures of which are incorporated herein by reference. More specifically for this invention, the curing agents are ideally oxazolidines, nitroalcohols, hexahydropyrimidines and their mixtures.
The fiber reinforcements will typically be glass, either as fibers or mats. The use of other fibrous reinforcements such as carbon, basalt, graphite or synthetic fibers or mats is within the scope of this invention. The critical parameter limiting the use of a given reinforcement with our systems is the processing temperature. If the melting/decomposition point of the reinforcement is above the processing temperature required by the resin system, then it may be used.
It will be clear from the examples that these novel formulations are an improvement over the known art in that a simple, liquid, two part resin (a) and hardener (b) package is sufficient for composite part manufacture with physical properties superior to a conventional resole while retaining the excellent FST properties of a classic phenolic system. Additionally, the demonstrated array of possible curing agents provides a broad spectrum of useful processing conditions for any given novolac resin system.
EXAMPLES
Durez PF novolac resin Varcum 29-607 was a commercial sample. The anisaldehydes, phenyl ether (DPE), anisole, phenol, resorcinol, the cresols, 4-t-butylphenol, 4-nonylphenol, zinc acetate, and all common laboratory acids, bases, solvents, and reagents were obtained from the Aldrich Chemical Company. Oxazolidines 5-ethyl-1-aza-3,7-dioxabicyclo[3.3.0]octane, 4,4-dimethyl-1-oxa-3-azacyclopentane, the nitroalcohol tris(hydroxymethyl)nitromethane, were all obtained from the ANGUS Chemical Company. 5-Hydroxymethyl-1-aza-3,7-dioxabicyclo[3.3.0]octane (M-3P) was obtained from Uniroyal. 2-Bromo-2-nitro-1,3-propanediol (Bronopol) was obtained from Dow Biocides. Other materials were synthesized as described in U.S. patent application Ser. No. 10/830,808 and co-pending U.S. patent application Ser. No. 10/383,272, the disclosures of which are incorporated herein by reference.
GPC Analyses:
GPC analyses were performed using a Waters Model 590 LC system with Plgel columns and THF eluent. Polystyrene standards were used for calibration.
DSC Analyses:
DSC analyses were performed using a TA Instruments Model Q100 differential scanning calorimeter. Scans for screening hardeners with Varcum 29-607 novolac were run from 25° C. to 400° C. at ΔT=10° C./minute with a nitrogen flow of 50 cc/minute. Non-hermetic aluminum pans were used. A small hole was punched in the top before crimping. Scans to obtain Tg data for low melting/liquid novolac resins were run from −50° C. to 150° C. at ΔT=10° C./minute with a nitrogen flow of 50 cc/minute using high volume (100 μl) aluminum pans. Scans for the analysis of the curing performance of formulations based on low melting/liquid novolac resins were run from 25° C. to 250° C. at ΔT=10° C./minute with a nitrogen flow of 50 cc/minute using high volume aluminum pans. After holding the samples at the maximum temperature for 10 minutes, the samples were cooled back to room temperature, then the scans were re-run to obtain Tg data.
Example 1—Reactive Diluent Blends
A series of physical mixtures of hardeners and phenolic monomers were made. The objective was to develop liquid blends of reactive novolac components (“reactive diluents”) that could be used to decrease the viscosity of novolac resins without introducing water or other organic solvents that would off-gas during curing, leading to voids and delamination in the cured parts. The blends made are shown in the Table below:













SAMPLE

MOLE



NO.
COMPONENTS
RATIO
PHYSICAL FORM







14A
Furfural/resorcinol
1:1
Undissolved resorcinol


14B
Furfural/resorcinol
2:1
Homogeneous low





viscosity liquid


14C
ZT/CS-1246
1:1
Undissolved ZT


14D
ZT/furfural/resorcinol
1:2:1
Gelled at room





temperature


14E
TN/furfural/resorcinol
1:2:1
Undissolved TN


14F
ZT/CS-1246/CS-1135
1:1:1
Low viscosity liquid


14G
TN/CS-1246/CS-1135
1:1:1
Low viscosity liquid


14H
TN/CS-1135
1:1
Low viscosity liquid


14I
ZT/furfural/m-cresol
1:2:1
Low viscosity liquid


14J
ZT/furfural/m-cresol
1:1:1.33
Low viscosity liquid


14K
ZT/furfural/m-cresol
1:1:1
Low viscosity liquid


14L
TN/furfural/m-cresol
1:2:1
Undissolved TN


14M
CS-1246/furfural/m-cresol
1:1:1
Low viscosity liquid









Example 2—Comparative DSC Data Survey—New Hardeners
In order to demonstrate the utility of the hardeners disclosed in this invention, a series of formulations were prepared using only one commercially available PF novolac resin (Durez Varcum 29-607). Any variations observed in the curing behavior of these formulations could therefore be attributed to the hardener/catalyst being evaluated. Hexa was used as the baseline for comparison since it is the hardener used most extensively in the industry.
The formulations were evaluated using a differential scanning calorimeter (DSC; TA Instruments Model Q100) to observe curing onset and peak temperatures and heats of curing for the curing events taking place. The DSC scans were run at ΔT=10° C./minute from 25° C. to 400° C. under a nitrogen flow of 50 cc/minute. The data obtained in this study are summarized in the Table below.
The classes of hardeners evaluated herein are those disclosed in U.S. patent application Ser. No. 10/830,808 and co-pending U.S. patent application Ser. No. 10/383,272, the disclosures of which are incorporated herein by reference.










NOVEL PHENOLIC RESINS


Comparative DSC Survey with Durez PF Novolac 29-607


TA Instruments Model Q 100 DSC


Run Conditions: 10 C./minute from 25 C. to 400 C. with


N2 at 50 cc/min.









CURING EVENTS










ONSET/
ONSET/









RESIN FORMULATION
PEAK C.
PEAK C.











HARDENER
PHR
CLASS
(HEAT, J/g)
(HEAT, J/g)














HEXA
5.39
Am-baseline
140/153 (69)
244/255 (72)


Hexa-BzCl
10
Hex-S
142/157 (70)


Hexa-BNM
8.6
Hex-S
129/164 (72)


NTA
8.6
AZA
180/197 (173)


NTA/IPHA
8.6/5.0
AZA-HA
170/192 (245)



8.6/2.5
AZA-HA
173/194 (133)



8.6/1.0
AZA-HA
173/194 (155)


ATA
15
AZA
 98/116 (17)
171/214 (78)



8.6
AZA
105/117 (15)
169/200 (77)


TN
11.11
NA
198/208 (254)


TN/DMTA
9.0/1.0
NA-Am
171/191 (106)


TN/Hexa
9.0/1.0
NA-Am
147/182 (80)
ca. 210/






ca. 230 (49)


NMPD
15
NA
198/212 (83)


NMPD/IPHA
10.0/5.0 
NA-HA
139/140 (3)
ca. 150/






196 (103)


Bronopal
20
NA
219/236 (302)


Bronopol/
15.0/5.0 
NA-HA
163/190 37)
212/


IPHA



241 (126)


Fur-IPHA
15
NIT
194/229 (170)


TN/Fur-IPHA
12.8/5.0 
NIT-NA
185/200 (177)



5.0/5.0
NIT-NA
189/203 (122)


Tere-IPHA
15
NIT
218/243 (182)


Glut-IPHA
15
NIT
191/229 (160)



7.5
NIT
196/229 (90)


Gly-IPHA
15
NIT
147/179 (255)


TN/Gly-IPHA
12.8/5.0 
NIT-NA
164/179 (226)



5.0/5.0
NIT-NA
157/179 (124)


Gly-PHA
15
NIT
130/165 (417)


TN/Gly-PHA
5.0/5.0
NIT-NA
153/174 (187)


Gly-EHA
15
NIT
128/161 (273)


TN/Gly-EHA
5.0/5.0
NIT-NA
142/169 (160)


NMP-An
15
NAm
158/181 (11)


TN/NMP-An
10.0/5.0 
NA-NAm
183/197 (201)


FUR/monoZE
25
OX
ca.88/ca.100
ca. 125/


FUR/ZE (1:2)



ca. 150


IPA-OZ
10
OZ
 87/113 (73)
ca. 150/






169 (61)





CLASS:


Am = amine


NAm = nitroamine


OX = oxazolidine


NIT = nitrone


HA = hydroxylamine


AZA = triazaadamantane


NA = nitroalcohol


Hex-S = hexamethylenetetramine salt


OZ = oxazine


Phen = substituted phenol salts






The DSC data shown in the Table above display a wide variation in curing behavior depending on the hardener used. This variation in cure behavior is important in developing formulations as it allows the cure onset temperature, formulation pot life and cure time to be optimized for a given application.
The hardener package and reactive diluent are only a portion of the full formulation required for composite applications. The properties of the phenolic novolacs also play a critical role in determining the utility of a given formulation. In order to fully define our invention, it was necessary to demonstrate the utility of a wide range of phenolic novolacs. As only a few variants of low molecular weight novolacs are commercially available, we synthesized a wide variety novolacs by using combinations of monomers.
Liquid or low melting (low Tg) novolac resins having a wide range of properties can be synthesized by the careful selection of components chosen from aromatic monomers, aldehydes, and phenolic monomers. Some specific examples of these classes of compounds include, but are not limited to the following:
Examples of Aromatic Monomers




Examples of Aldehydes





Examples of Phenolic Monomers





In order to achieve certain desirable properties of the cured or uncured novolac resins one or more components from each of the classes above may be incorporated. The resins may be synthesized either by one-step or two-step processes with acidic, basic, or Lewis acid catalysts as appropriate for the reactivities of the chosen components.
Example 3—Two-Step Synthesis of Novolac Resins Containing Aromatic Monomers and Alternative Aldehydes
Novolac Resins Containing Aromatic Monomers and Alternative Aldehydes (Method A): The general two-step procedure described below was used to synthesize several resins that incorporated DPE and/or anisole. The same procedure was followed in the preparation of resins that contained m- and/or p-anisaldehyde in place of formaldehyde. Resin characterization data are summarized in the Table below.
A 500 mL jacketed resin kettle was charged with 34.04 g (0.20 moles) of DPE, 21.63 g (0.20 moles) of anisole, 73.11 g (1.22 moles) of glacial acetic acid, and 50.37 g (0.62 moles) of 37 wt. % aqueous formaldehyde solution. The solution was stirred under a nitrogen blanket, then 10 mL of concentrated sulfuric acid were added. The solution turned light olive green. The solution was stirred under nitrogen at 95° C. for 24 hours, then 41.5 g (0.44 moles) of phenol were added in 4 portions over a 15 minute period. Heating at 95-100° C. was continued for a further 10 hours. The reaction mixture was cooled to room temperature, then 250 mL of ethyl acetate were added. The solution was filtered free of a small amount of insoluble solids. The bulk of the acetic and sulfuric acids were neutralized—initially by the portionwise addition of solid sodium bicarbonate, and finally by the addition of saturated aqueous sodium bicarbonate solution. The addition of 400 mL of water allowed the mixture to separate into a lower, aqueous layer and an upper, product solution in ethyl acetate. The product solution was dried over anhydrous magnesium sulfate, then the solvent was removed by rotary evaporation to give 100.4 g (93%) of product as a clear, brown, viscous resin. GPC analysis gave Mw=2223 and MN=718. DSC analysis showed a Tg=8° C.
Example 4—One-Step Synthesis of Novolac Resins
One-Step Synthesis With Zinc Acetate Catalyst (Method B): The general one-step procedure using zinc acetate catalyst described below was used to synthesize several resins used in this study. Resin characterization data are summarized in the Table below.
A 3-neck flask equipped with a heating mantle, mechanical stirrer, distillation head with graduated receiver, thermocouple for temperature control and a N2 blanket was charged with p-cresol (34.86 g, 0.30 mol), paraformaldehyde (6.0 g, 0.2 mol) and zinc acetate dihydrate (0.90 g, 0.004 mol). The mixture was brought to 105° C. where a homogeneous solution was obtained. After 2 hours, the mixture was warmed to 125° C. where water began to distill out of the reactor. Vacuum was slowly applied to the reaction mixture to induce the remainder of the water to distill. A vacuum of 40 torr had been achieved in 20 minutes, and this was maintained for an additional 5 minutes. The reaction was terminated via cooling under N2; approximately 3.5 mL water had been collected (3.6 mL theory). The product was an opaque, yellow-brown solid. GPC analysis gave Mw=595 and MN=334. DSC analysis showed a Tg=30° C.
One-Step Synthesis With Oxalic Acid Catalyst (Method C): A 3-neck flask equipped with a heating mantle, mechanical stirrer, distillation head with graduated receiver, thermocouple for temperature control and a nitrogen blanket was charged with phenol (28.7 g, 0.31 mol), 4-t-butylphenol (45.29 g, 0.31 mol), formaldehyde (37.2 mL of 37% aqueous solution, 0.5 mol) and oxalic acid (0.9 g, 0.01 mol). The mixture was brought to 80° C. where a homogeneous solution was obtained. After 80 minutes the mixture had become hazy. After 180 minutes, the mixture was warmed to 100-110° C. where water distilled out of the reactor. After 35 minutes, approximately 25 mL of water had been collected (theoretical water=34 g). Vacuum was slowly applied to the reaction mixture to induce the remainder of the water to distill. A vacuum of 170 torr had been achieved in 15 minutes, and this was maintained for an additional 15 minutes. The reaction was terminated via cooling under N2; 35 mL distillate (34 mL water, 1 mL oil phase) had been collected. The product was a solid, off-white, translucent mass. GPC analysis gave Mw=979 and MN=425. DSC analysis showed a Tg=32° C.
As is obvious to anyone skilled in the art of resin preparation, the resin systems will vary in pH depending on the method of preparation. For the purposes of this invention, the resin pH should be in the range of 8-12. Adjustments to the resin formulation to increase, or decrease pH may be made. Typical agents used to increase resin pH would include (but not limited to) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide; amine compounds such as triethylamine, DABCO, 1,1,3,3-tetramethylguanidine, DBN, DBU, alkoxides, phenoxides, quaternary ammonium hydroxides and other organic or inorganic bases. Agents useful for decreasing resin pH would include mineral acids, sulfuric acid, alkyl sulfonic acids, aryl sulfonic acids, carboxylic acids, phosphoric acid, and other organic and inorganic acids.
While not preferred, it is also within the scope of this patent that a resin outside the pH range of 8-12 could be utilized. In these cases, the pH adjustments, utilizing the agents described above, may be made directly on the final formulations.










NOVEL PHENOLIC RESINS


Compositions and Properties of Liquid/Low Melting Novolac Resins



















MOLECULAR






Resin

MOLE
SYNTHESIS
WEIGHT
Tg

RESIN
NTBK
















No.
POLYMER COMPOSITION
RATIO
METHOD
MW
MN
° C.
TM ° C.
FORM
REF



















15A
phenyl ether/formaldehyde/
1:1.55:1.1
A
1774
761
9
(none)
viscous
2221-31



phenol






liquid


15B
anisole/p-anisaldehyde/phenol
1:1.55:1.15
A
731
161
33
ca.50
solid
2221-19,











27


15C
phenyl ether/anisole/
0.5:0.5:1.55:
A
2223
718
3
(none)
viscous
2221-37



formaldehyde/Phenol
1.1





liquid


15D
anisole/p-anisaldehyde/m-
1:0.78:0.78:
A
1272
1205
41
ca.50
solid
2221-43



anis-aldehyde/phenol
1.1


15E
glutaraldehyde/phenol
1:3.75
A
5529
449
37
ca.69
solid
2221-49


15F
cyclohexanedicarboxaldehyde/
1:3.75
A
2733
387
96
ca.113
solid
2221-59



Phenol


16A
paraformaldehyde/p-cresol
2:3
B
595
3343
30
(none)
solid
1641-48


16B
paraformaldehyde/p-cresol/
2:1:1:1
B
668
416
27
(none)
solid
1641-49



o-cresol/4-t-butylphenol


16C
paraformaldehyde/phenol/
5:3:3
B
2559
809
37
(none)
solid
1641-50



4-nonylphenol


16D
paraformaldehyde/phenol/
4:2.5:2.5
B
1774
267


tacky solid
1641-57



4-t-butylphenol


16E
formaldehyde/phenol
5:6
C
4869
687
53
86
solid
3178-24


16F
formaldehyde/phenol/
5:3.1:3.1
C
979
425
32
53
solid
3178-26



4-t-butylphenol


16G
formaldehyde/phenol/
5:3.1:3.1
C
1089
471
−9
(none)
taffy-like
3178-66



4-nonylphenol


16H
formaldehyde/phenol/m-
3:1:2:1
C
33743
894
−4
(none)
soft solid
1641-69



cresol/4-nonylphenol


16I
paraformaldehyde/bisphenol-
2:2:1
C
1629
750
37
54
glassy
1641-70



A/4-nonylphenol






solid









Example 5—Comparative Formulation Survey of Low Melting/Liquid Novolac Resins
A key objective of this invention was the development of novolac resin formulations that were free of water, contained minimal amounts of inert solvents, and that demonstrated reasonable flow properties at temperatures of 25-40° C. These formulations are anticipated to be useful in fiber reinforced composite applications requiring the coating of fibers with a thermosetting liquid resin. Pultrusion and filament winding are two such examples of composite applications.
A large number of novel hardeners have been disclosed herein, and a significant number of reactive diluent blends have been described. Combining the reactive diluents/hardeners with the varieties of novolac resins prepared above creates a vast number of formulations that could be generated from these components. Therefore, for the purpose of demonstrating the concept, this formulation survey was conducted using a representative selection of components. No attempt was made to optimize the formulations, and most of the formulations are not balanced. That is, most of the formulations are deficient in hardener equivalents with respect to the resin acceptor capacity.
Formulation flow characteristics were observed at both 40° C. and at 70° C., although those at the lower temperature were of greater interest. The formulation survey data are summarized in the Table below.










Compositions and Properties of Liquid/Low Melting Novolac Resin Formulations





















Formulation

HARDENER/

TEMP.,

NTBK.


No.
RESIN
REACTIVE DILUENT
PHR
° C.
FORMULATION PROPERTIES
REF.





18-1
15A
Ox1
30
40
viscous, clear, light yellow, flows freely
02221-68B


18-2
15A
IPA-OZ
30
40
extremely viscous, clear, dark brown, no flow
02730-13C


18-3
15A
NA2
30
40
viscous, clear, orange, flows readily
02730-14C


18-4
15B
Ox1
30
40
very viscous, clear, deep red, almost no flow
02221-68C


18-5
15B
IPA-OZ
30
40
extremely viscous, deep red, no flow
02730-13B


18-6
15B
NA2
30
40
extremely viscous, clear, deep red, no flow
02730-14B


18-7
15C
Ox1
30
40
viscous, clear, light amber, flows freely
02221-68D


18-8
15C
IPA-OZ
30
40
extremely viscous, clear, dark brown, no flow
02730-13D


18-9
15C
NA2
30
40
viscous, clear, orange, flows freely
02730-14D


18-10
15D
Ox1
30
40
very viscous, clear, deep red, almost no flow
02221-68E


18-11
15D
IPA-OZ
30
40
extremely viscous, deep red, no flow
02730-13E


18-12
15D
NA2
30
40
extremely viscous, deep red, no flow
02730-14E


18-13
15E
Ox1
30
40
very viscous, clear, brown, almost no flow
02221-68F


18-14
15E
IPA-OZ
30
40
wet solid
02730-13F


18-15
15E
NA2
30
40
extremely viscous, clear, dark brown, no flow
02730-14F


18-16
15F
NA2
30
40
wet solid
02730-14G


18-17
16A
Ox1
30
70
extremely viscous, cloudy yellow, no flow
02730-18A


18-18
16A
IPA-OZ
30
70
extremely viscous, incomplete mix, brown, no flow
02730-19A


18-19
16A
NA2
30
70
wet solid







HARDENER/


No.
RESIN
REACTIVE DILUENT
PHR
° C.
FORMULATION PROPERTIES
REF.





18-1
15A
Ox1
30
40
viscous, clear, light yellow, flows freely
02221-68B


18-2
15A
IPA-OZ
30
40
extremely viscous, clear, dark brown, no flow
02730-13C


18-3
15A
NA2
30
40
viscous, clear, orange, flows readily
02730-14C


18-4
15B
Ox1
30
40
very viscous, clear, deep red, almost no flow
02221-68C


18-5
15B
IPA-OZ
30
40
extremely viscous, deep red, no flow
02730-13B


18-6
15B
NA2
30
40
extremely viscous, clear, deep red, no flow
02730-14B


18-7
15C
Ox1
30
40
viscous, clear, light amber, flows freely
02221-68D


18-8
15C
IPA-OZ
30
40
extremely viscous, clear, dark brown, no flow
02730-13D


18-9
15C
NA2
30
40
viscous, clear, orange, flows freely
02730-14D


18-10
15D
Ox1
30
40
very viscous, clear, deep red, almost no flow
02221-68E


18-11
15D
IPA-OZ
30
40
extremely viscous, deep red, no flow
02730-13E


18-12
15D
NA2
30
40
extremely viscous, deep red, no flow
02730-14E


18-13
15E
Ox1
30
40
very viscous, clear, brown, almost no flow
02221-68F


18-14
15E
IPA-OZ
30
40
wet solid
02730-13F


18-15
15E
NA2
30
40
extremely viscous, clear, dark brown, no flow
02730-14F


18-16
15F
NA2
30
40
wet solid
02730-14G


18-17
16A
Ox1
30
70
extremely viscous, cloudy yellow, no flow
02730-18A


18-18
16A
IPA-OZ
30
70
extremely viscous, incomplete mix, brown, no flow
02730-19A


18-19
16A
NA2
30
70
wet solid





Formulation

HARDENER/

TEMP.,

NTBK.


No.
RESIN
REACTIVE DILUENT
PHR
° C.
FORMULATION PROPERTIES
REF.





18-43
16F
Ox1
30
70
extremely viscous, clear light brown, almost no flow
02730-18E


18-44
16F
IPA-OZ
30
70
extremely viscous, incomplete mix, light brown, no
02730-19E







flow


18-45
16F
NA2
30
70
viscous, clear dark red brown, flows readily


18-46
16F
NA2
30
40
flows readily


18-47
16F
NA3
30
70
very viscous, clear red, flows slowly
02730-22B


18-48
16F
NA3
30




14A
10
70
extremely viscous, nearly black, no flow
02730-24C


18-49
16F
NA3
30




14A
10
40
extremely viscous, nearly black, no flow
02730-28C


18-50
16F
NA3
30




14B
10
70
extremely viscous, nearly black, no flow
02730-24D


18-51
16F
NA3
30




14B
10
40
extremely viscous, nearly black, no flow
02730-28D


18-52
16F
14C
30
40
extremely viscous, clear light brown, no flow
02730-44A


18-53
16F
14C
30
70
extremely viscous, clear light brown, no flow
02730-45A


18-54
16F
14F
30
40
extremely viscous, clear light brown, no flow
02730-44B


18-55

14F
30
70
extremely viscous, clear light brown, no flow
02730-45B


18-56
16F
14G
30
40
extremely viscous, clear brown, no flow
02730-44C


18-57

14G
30
70
extremely viscous, clear brown, no flow
02730-45C


18-58
16F
14H
30
40
extremely viscous, clear brown, no flow
02730-44D


18-59

14H
30
70
extremely viscous, clear brown, no flow
02730-45D


18-71
16G
14G
30
40
extremely viscous, clear dark brown, no flow
02730-44H


18-72
16G
14G
30
70
extremely viscous, clear dark brown, no flow
02730-45H


18-73
16G
14H
30
40
extremely viscous, clear dark brown, no flow
02730-44I


18-74
16G
14H
30
70
extremely viscous, clear dark brown, no flow
02730-45I


18-75
16G
14I
30
40
extremely viscous, clear brown, flows slowly
02730-44J





30
70
extremely viscous, clear brown, flows slowly
02730-45J


18-76
16B/15C
NA2
30
40
very viscous, clear brown, flows
02730-26A



3:1, wt.


18-77
16B/15C
NA2
30



3:1, wt.
14A
10
40
very viscous, clear brown, flows
02730-26B


18-78
16B/15C
NA2
30



3:1, wt.
14B
10
40
very viscous, clear brown, flows
02730-26C


1641-69
16H
Ox1
30
70
extremely viscous, clear amber, no flow
02730-60A



16H
NA2
30
70
incomplete mixing
02730-60B



16H
14B
30
70
extremely viscous, nearly black, no flow
02730-60C


1641-70
16I
Ox1
30
70
extremely viscous, clear amber, no flow
02730-60D



16I
NA2
30
70
incomplete mixing
02730-60E



16I
14B
30
70
extremely viscous, nearly black, no flow
02730-60F





Ox1 = 5-ethyl-1-aza-3,7-dioxabicyclo[3.3.0]octane


NA2 = 60/40 mixture (w/w) of 2-ethyl-2-nitro-1,3-propanediol with 2-nitro-1-butanol


NA3 = NA2 diluted with 25% (w/w) tris(hydroxymethyl)nitromethane






A number of generalizations can be made from the formulation data in the Table:

    
    
        It is clear from the results that the viscosity of the starting resin does not predict the viscosity of the formulation prepared with it. This is clearly demonstrated by formulation 18-2 in which novolac 15A—a viscous liquid—was blended with IPA-OZ—an oil. The resulting formulation was more viscous than the resin itself.
        Formulation flow properties did not change as much as anticipated upon increasing the temperature from 400 to 70° C.
        The most effective hardeners/reactive diluents in generating formulations that exhibited flow at 40° C. were Ox1 and NA2.
        Resin molecular weight was not a good predictor of formulation viscosity.
        The novolac resin most readily blended into flowable formulations was 16G.
        Resin formulation viscosities can be improved by blending with lower viscosity resins. Formulations 18-76, 77, and 78 show blends of resins 16B with 15C that flow readily at 40° C. Similar formulations containing only 16B did not flow at 40° C. Given the results from Formulation 18-2, this is not an obvious outcome.
    
    


Example 6—DSC Curing Data For Selected Low Melting/Liquid Novolac Resin Formulations
Those resin formulations that exhibited flow at 40° C. or 70° C. were selected for DSC analysis to determine their curing behavior. Some resin formulations that were too viscous to flow were also included. The reason for doing so was that the survey formulations were not optimized, and some of the very viscous formulations were based on resins that did generate other flowable formulations.
Curing performance data were obtained by running the DSC analyses at ΔT=10° C./minute from 25° C. to 250° C. under a nitrogen flow of 50 cc/minute. The samples were then held at 250° C. for 10 minutes, and then cooled to −50° C. The Tg values of the cured formulations were then determined by running the DSC analyses at ΔT=10° C./minute from −50° C. to 250° C. under a nitrogen flow of 50 cc/minute. The samples were then cooled back to −50° C., and again re-heated to 250° C. as before. High volume (100 μL) pans were used for these analyses.
In many of these analyses, the curing events were not completed at the 250° C. temperature limit of the scan. In these cases, it was not possible to determine the heats of curing (J/g) since no baseline could be determined.
In some experiments, it was easier to detect the Tg during the cooling cycle of the run than in the re-heat cycle. In other experiments, no baseline deviations could be observed in either the heating or the cooling cycles. These samples either had Tg values of >250° C. or they were lower in temperature but too small to be detected. The Tg value was reported as “none” for these cured formulations.
The results of these curing studies are summarized in the Table below.










NOVEL PHENOLIC RESINS


CURE CONDITIONS: Scan from 25 C. to 250 C. at 10 C./minute using high volume


pans; hold at 250 C. for 10 minutes; cool back to 25 C.; run Tg scan from −50 C. to 250 C..










DSC CURE STUDIES
DSC CURING EVENTS

















FORMULATION
ONSET/PEAK
ONSET/PEAK
CURED
NTBK


Formulation

Identification
TEMP, ° C.
TEMP, ° C.
RESIN
REF


No.
RESIN
from ex. 5
(HEAT, J/g)
(HEAT, J/g)
Tg, ° C.
DSC DATA





19-1
16G
18-62
143/200 (105)

(none)
2074-28-20


19-2
16G
18-63
227/242

137
2074-28-21


19-3
16G
18-64
226/244

141
2074-28-22


19-4
16G
18-65
225/235

156
2074-28-23


19-5
16G
18-66
226/235

170
2074-28-24


19-6
16G
18-75
162/201 (19)

(none)
2074-29-23


19-7
16G
18-73
132/222 (64)

(none)
2074-29-22


19-8
16G
18-67
153/206(111)

(none)
2074-29-21


19-9
15A
18-1
215/243

68, 176
2074-28-7


19-10
15A
18-3
211/222
245
115
2074-28-8


19-11
15C
18-7
209/233

70 (?)
2074-28-9


19-12
15C
18-9
208/231

130
2074-28-10


19-13
16B
18-22
193/210(315)

(none)
2074-29-6


19-14
16B/15C
18-76
189/212(461)

160
2074-28-12



3:1


19-15
16B/15C
18-77
217/227
250
130
2974-28-13



3:1


19-16
16B/15C
18-78
209/221
244
147
2074-28-14



3:1


19-17
16F
18-46
226/237

172
2074-28-15


19-18
16F
18-47
222/233

165
2074-28-16


19-19
16F
18-49
180/226

(none)
2074-29-16









The resin formulations selected for DSC evaluations contained at least 30 phr of hardeners/reactive diluents, and most exhibited resin flow at 40° C. Formulations 18-63 and 18-64 had resin flow even at room temperature. All of these 100% solids, low-melting/liquid resin formulations showed good curing behavior by DSC.
Most of the formulations showed a single curing event. Curing onset temperatures ranged from as low as about 140° C. to as high as about 225° C., with curing peak temperatures ranging from 200° C. to as high as 250° C. As noted earlier, total heats of curing (J/g) were not possible to obtain in many experiments because the curing events were not completed before the 250° C. temperature limit of the experiment was reached, so no baseline could be determined.
As noted above, Tg scans were run after holding the formulations at 250° C. for 10 minutes. In many experiments, no baseline deviations were observed either during the heating or cooling cycles of the experiments—thus, no Tg observed below 250° C. In other experiments, only a weak transition—usually at <100° C.—could be observed during one of the cycles. This was recorded as a Tg value, though it is questionable.
The data in the Table show a considerable variation in curing performance and in Tg values, even for a given resin. This confirms that the choice of hardeners/reactive diluents can have a dramatic effect not only on the curing behavior of the formulations, but ultimately on the cured resin physical properties. This is in marked contrast to novolac resins cured using formaldehyde, paraformaldehyde, or hexa as the hardener.
Example 7—Composite Plague Preparation
It can be argued that, while the DSC confirms that these high solids, low-melting/liquid novolac resin formulations exhibit exothermic events, they may represent hardener/resin decomposition rather than curing reactions. Similarly, the increase in—or absence of—Tg values can be attributed to char formation rather than to cured resin. The definitive demonstration that these high solids, low-melting/liquid novolac resin formulations are useful in composite applications was to fabricate composite plaques. The resin selected for this demonstration was 16F, formulated with an Ox1—furfural—m-cresol hardener/reactive diluent combination.
Formulation Preparation: Novolac resin 16F (15 g) was weighed into a 4-oz jar and 3.4 g of Ox1 were added. The mixture was warmed in an oven at 70° C. to give a clear, viscous solution. While still at 70° C., a mixture of 5.44 g of Ox1, 3.65 g of furfural, and 4.11 g of m-cresol were added. The mixture was stirred at 70° C. to give a clear yellow solution. After cooling to room temperature, the formulation had the approximate consistency of honey.
Plague Preparation: Woven fiberglass cloth (AircraftSpruce, #7781) was cut into 6-inch squares weighing approximately 6.9 g each. Plaques were constructed by placing a square of glass cloth onto a flat surface. Then 3-4 g of resin formulation were drizzled evenly over the cloth. The resin was spread over the entire surface of the square and worked into the fabric using a 4-inch ink roller. Four pieces of resin-impregnated glass cloth were then stacked in sandwich form and were compressed using the roller. The sandwich was then placed between two aluminum foil sheets and then between two 1/16-inch aluminum plates. The assembly was placed into a 185° C. forced air oven. After curing for 15 minutes, the composite plaque was removed and was cut in half. One half of the plaque was cooled to room temperature (Plaque A), and the other was cured for an additional 15 minutes (Plaque B).
Plaque A was a stiff, golden brown composite with no residual odor or tack. Plaque B was a stiff, dark brown composite, also having no residual odor or tack. The rigidity of the plaques and the absence of tack or odor indicated that the formulation was fully cured.
Example 8—Rapid Curing of Composite Plagues
For pultrusion, it is important to have a rapid cure formulation such that reasonable manufacturing rates can be achieved. Phenolic resoles are pultruded at rates varying from 10′′/min up to 32′′/min. As typical pultrusion die lengths are 36′′, in order to get a fully cured part at a rate of 18′′/minute, it is necessary to achieve full cure in <2 minutes. A subset of our novel fully formulated high solids novolac resin systems were tested to see what temperature range would be required to achieve full cure in this time frame. Extent of cure was ascertained using visual and tactile impressions. The results are collected in the table.

















Novolac
Curing
Reactive
Cure
Cure



Experiment
Resin (R1)
Agent(s)
Diluent(s)
Temp.
Time
Result







2992-15
33.5 g
Ox1 (18.1)
Furfural (7)
185
5 min
Fully cured




Ox3 (7)
m-cresol
185
2 min
Undercured





(7)
205
2 min
Undercured


2992-16
33.5 g
Ox1 (26.7)
m-cresol
205
3 min
Fully cured





(12.4)
205
1.5
Undercured






225
1.5
Fully cured


2992-18
33.3 g
Ox1 (12.7)
m-cresol
185
1.5
Fully cured




Ox2 (23)
(12.4)


2992-26
   50 g*
HHP (18)
m-cresol
120
3
Fully cured




LNA-25 (18)
(16.6)
120
1.5
Undercured


2992-36
33.3**
Ox1(8)
11.1
205
1
Fully cured




HHP (12.8)


2992-45
37.5
Ox1 (7.5)
Furfuryl
225
1.5
Fully cured





alcohol





(12.5)


2992-46
37.5
Ox1 (12.9)
RD1 (12.5)
225
0.75
Fully cured






225
0.33
Undercured





*contained 10 mL methanol in addition to the 50 g resin


**contained 5 mL methanol in addition to the 33.3 g resin


Ox3 = Bonding Agent M-3P


HHP = N,N′-bis(2-propyl)-5-hydroxymethyl-5-nitro-1,3-hexahydropyrimidine


LNA25 - mixture of 2-nitro-2-ethyl-1,3-propanediol (0.45 mol eq), 2-nitro-1-butanol (0.3 mol eq) and tris(hydroxymethyl)nitromethane (0.25 mol eq) in methanol (25% w/w)






Clearly the data indicate that reasonable pultrusion rates (e.g. at least 12′′/min) should be obtainable with all of the formulations if the temperature is sufficiently high. Additionally, as expected, the extent of cure for a given cure cycle increases with higher temperature.
Example 9—Pultrusion Studies
Pultrusion studies were performed on a Pulstar 804 instrument using a 1′′×1⁄8′′ die profile. Electric platens were used to heat the 36′′ die in three independent 12′′ zones. Johns Manville 507A continuous glass rovings were used; 32 ends of glass were used to create a part with 68% (vol/vol) glass/32% resin. Three-point flexural testing was performed on 5′′ long specimens, with a span width of 4 inches, on an MTS mechanical tester. Three identical parts were subjected to testing and the average value reported. The procedure followed was ASTM D-790-90.
Based on the results obtained in the previous examples, a series of formulations were prepared and tested in actual pultrusion trials. Formulations with 100% solids and formulations containing minimal amounts of inert solvents were used. A comparison to a commercially available resole-based phenolic pultrusion resin was made. The pultrusion processability, pultrusion speed, part finish, and mechanical integrity of the completed part were evaluated. The formulations tested are shown in the Table below, and in all cases, viable solid parts were obtained.




















Reactive

Release


Formulation
Resin
Oxazolidine
Nitroalcohol
Diluent
Solvent
Agent







ANGA01
2603 (R1)
1062 (Ox1)
250 (NA1)
None
459
 76 (RA1)


ANGA02
2603 (R1)
1062 (Ox1)
250 (NA1)
None
459
135 (RA1)


ANGA03
3825 (R1)
1676 (Ox1)
None
None
675
186 (RA1)


ANGA04
3825 (R1)
1676 (Ox1)
None
1000
675
186 (RA1)






(RD1)


ANGA05
2475 (R1)
1386 (Ox1)
None
400 (RD2)
225
112 (RA1)


ANGA06
2475 (R1)
1386 (Ox1)
None
400 (RD2)
225
112 (RA1)


ANGA07
2250 (R1)
1550 (Ox1)
None
750 (RD2)
None
114 (RA1)


ANGA08
2550 (R1)
 560 (Ox1)/
None
None
450
119 (RA1)




1010 (Ox2)


ANGA09
2550 (R1)
960 (Ox1)
196 (NA2)
None
450
106 (RA1)


ANGA10
2550 (R1)
1120 (Ox1)
None
None
658**
120 (RA1)


ANGB01
2357 (R2)
1083 (Ox1)
None
435 (RD1)
516
114 (RA1)


ANGB02
2355 (R2)
1080 (Ox1)
None
422 (RD1)
516
112 (RA2)


ANGB03
2354 (R2)
1080 (Ox1)
None
421 (RD1)
515
136 (RA3)


ANGB04
2354 (R2)
1081 (Ox1)
None
420 (RD1)/
565
137 (RA3)






121






(RD3)


ANGB05
3060 (R2)
1409 (Ox1)
None
1106
735
196 (RA3)






(RD1)/






156 (RD3)


ANGB07
2706 (R2)
 745 (Ox1)
None
163 (RD3)
678
135 (RA3)


ANGB08
3239 (R2)
1495 (Ox1)
None
None
637
227 (RA3)


ANGC01
3239 (R2)
1490 (Ox1)
None
None
642
170 (RA3)


ANGC02
3239 (R4)
1500 (Ox1)
None
None
804
170 (RA3)


ANGC03
3239 (R2)
1490 (Ox1)
None
None
642
170 (RA4)


ANGC04
3239 (R2)
1490 (Ox1)
None
None
642
170 (RA5)


ANGC06
3221 (R5)
1480 (Ox1)
None
None
818
170 (RA3)


ANGC07
3239 (R4)
1190 (Ox1)
None
None
789
165 (RA3)


ANGC08
3239 (R4)
1785 (Ox1)
None
None
816
181 (RA3)


ANGC09
3239 (R4)
1500 (Ox1)
None
None
804
170 (RA5)


ANGC10
3239 (R2)
1490 (Ox1)
None
None
692*
170 (RA3)


ANGC11
3239 (R2)
1490 (Ox1)
None
None
642
170 (RA3)


ANGC12
3239 (R2)
1190 (Ox1)
None
None
692
157 (RA3)


ANGC13
3239 (R4)
1500 (Ox1)
None
None
804
170 (RA3)


Control
5788 (R3)
None
None
None
Unknown
174 (RA1)





R1 - Phenolic novolac with minimal residual phenol (<1%), resin as prepared (non-neutralized)


R2 - Phenolic novolac with residual phenol (<10%), resin as prepared (non-neutralized)


R3 - Cellobond J20 resole resin in water


R4 = Phenolic novolac with residual phenol (<10%), resin partially neutralized with base


R5 = Phenolic novolac with residual phenol (<10%), resin partially neutralized with base


Ox1 = 5-ethyl-1-aza-3,7-dioxabicyclo[3.3.0]octane


Ox2 = 4,4-dimethyl-1-oxa-3-azacyclopentane


NA1 = Tris(hydroxymethyl)nitromethane in water (50/50 by wt.)


NA2 = 60/40 mixture (w/w) of 2-ethyl-2-nitro-1,3-propanediol with 2-nitro-1-butanol


RD1 = Durite SL-486A phenolic resole resin


RD2 = m-cresol


RD3 = Low MW, solid phenolic novolac prepared from phenol/formaldehyde/hexamethylenetetramine


RA1 = Axel 1850HT


RA2 = Axel XP Pul14D


RA3 = Techlube 721 ZL


RA4 = Axel XPPul-14K


RA5 = Axel XPPul-14PP


*additionally contained 120 g 1,1,3,3-tetramethylguanidine


**additionally contained 510 g solid aluminum tri-hydrate powder as a filler.






The surface finish of the parts was in large part attributable to the release agent used. The parts made using RA1, RA2, RA4 and RA5 had a significant amount of surface dust, although once cleaned the parts were smooth. Parts made using RA3 did not have any dusting, and were very smooth and glossy.
The successful processing of the formulations was also affected by the selection of release agent. Again, RA1, RA2, RA4 and RA5 were similar in that while they allowed successful pultrusion, process changes or upsets often caused part failure in the die. Release agent RA3 was shown to provide much more latitude in varying pultrusion parameters.
The effects of pultrusion process parameters on part integrity are discussed in subsequent examples.
Example 10—Effect of Temperature on Cure Speed
Using three nearly identical formulations, a study of cure speed versus die temperatures was conducted. Analogous to the plaque curing experiments, it was seen that an increase in die temperature allowed an increase in pull rates while still generating a solid part.
















Zone 1
Zone 2
Zone 3





(die
(center of
(die


Formulation
entrance)
die)
exit)
Pull Speed
Result







ANGA03
400
450
425
18′′/min
Solid part



400
450
425
24′′/min
Soft part


ANGB08
460
485
485
24′′/min
Solid part



490
510
510
32′′/min
Solid part



490
510
510
36′′/min
Solid part



490
510
510
40′′/min
Soft part


ANGC11
525
525
525
44′′/min
Solid part



525
525
525
48′′/min
Solid part



525
525
525
52′′/min
Soft part


Cellobond
375
400
400
12′′/min
Solid part


J20


Control*





*Processed using the recommended settings from the manufacturer.






Example 11—Effect of Resin/Hardener Ratio
Using pultrusion conditions shown to produce fully cured, viable parts for each formulation, a demonstration of the effect of resin/hardener ratio on physical properties of the cured parts was performed. As can be seen in the table, the ratio of resin/hardener may be varied significantly while still maintaining physical properties superior to the resole control.
















Resin/







Hardener
Peak



Ratio
Load
Peak Stress
Modulus
% Strain


Formulation
(w/w)
(lbs)
(ksi)
(Mpsi)
at Break







ANGC07
2.72
536
192
7.2
2.9


ANGC08
1.81
480
169
7.0
2.5


ANGC13
2.16
563
205
7.2
3.1


Cellobond
Not
441
154
7.0
2.4


J20 Control
Applicable









Example 12—Effect of Resin Neutralization
As discussed above, to get within the desired pH range, the resin may be either used as manufactured, acidified or basified depending on the method of manufacture. As seen in the table, we have demonstrated that resin treated with base can have an impact on the rate of pultrusion and the final part integrity.

















Base added
Maximum Pull
Peak Load
Peak Stress
Modulus
% Strain at


Formulation
to Resin
Rate @ 525 F.
(lbs)
(ksi)
(Mpsi)
Break







ANGC11
No
<48′′/min
531
193
7.1
2.9


ANGC06
Yes
>72′′/min
373
130
6.8
1.9









Example 13—Effect of Reactive Diluents
It may be desirable to add reactive diluents or alternative cross-linking agents to a formulation to vary viscosity, solvent level, mechanical properties of the cured part, reactivity, formulation cost or other considerations. As shown in the table, a variety of materials may be added while still maintaining the ability to produce viable pultruded parts. All formulations shown produced solid, fully cured, viable parts.




















Reactive

Release


Formulation
Resin
Oxazolidine
Nitroalcohol
Diluent
Solvent
Agent







ANGA02
2603 (R1)
1062 (Ox1)
250 (NA1)
None
459
135 (RA1)


ANGA04
3825 (R1)
1676 (Ox1)
None
1000 (RD1)
675
186 (RA1)


ANGA05
2475 (R1)
1386 (Ox1)
None
 400 (RD2)
225
112 (RA1)


ANGA07
2250 (R1)
1550 (Ox1)
None
 750 (RD2)
None
114 (RA1)


ANGA08
2550 (R1)
 560 (Ox1)/
None
None
450
119 (RA1)




1010 (Ox2)


ANGA09
2550 (R1)
 960 (Ox1)
196 (NA2)
None
450
106 (RA1)


ANGB04
2354 (R2)
1081 (Ox1)
None
 420 (RD1)/
565
137 (RA3)






121 (RD3)


ANGB05
3060 (R2)
1409 (Ox1)
None
1106 (RD1)/
735
196 (RA3)






156 (RD3)


ANGB07
2706 (R2)
 745 (Ox1)
None
 163 (RD3)
678
135 (RA3)


ANG
2550 (R1)
1120 (Ox1)
None
None
658*
120 (RA1)


A10





*Additionally contained 510 g solid aluminum tri-hydrate as a filler






Example 14—FST Testing
To demonstrate the excellent FST properties obtainable with the novel systems of our invention, ASTM E662-95 testing was performed on parts generated via the pultrusion of formulations ANGA03 and ANGA04. Testing in both flaming and non-flaming mode was completed. The results are shown in the table:
















Dm (ave)
Dm (ave)



Formulation
Flaming Mode
Non-Flaming mode




















ANGA03
13.04
11.57



ANGA04
9.52
6.22










These results clearly show that our two part resin formulation based on resin (a) and hardener (b) is sufficient to provide composite parts with outstanding FST properties. The use of a reactive diluent has also been shown to be potentially advantageous in further improving FST performance.
Example 15—Filament Winding
The pultrusion examples clearly demonstrate that once applied to a fibrous substrate, the formulations of this invention may be cured via the application of heat to form a solid part. Filament winding is another manufacturing technique often used to prepare complex composite parts. The formulations of this invention are equally applicable to the manufacture of filament wound composite parts.
As a demonstration of filament winding, continuous glass roving was fully impregnated with formulation ANGC13 and wound at room temperature onto a cylindrically shaped mandrel. The mandrel was placed into an oven and, with continued rotation, warmed from 25 to 125 C over 30 minutes, then held at 125 C for an additional 20 minutes. After cooling, the fully cured, solid composite cylindrically shaped tube was removed from the mandrel.

## Claims

1. A composition for the manufacture of composites comprising:
i) a formulated resin system comprising:
a. a novolac resin prepared from a phenolic compound and an aldehyde, wherein the phenolic compound is selected from the group consisting of phenol, bisphenol, phloroglucinol, cresols, alkyl phenols, phenol ethers, tannins and lignins, and wherein the ratio of aldehyde to phenolic compound is less than one; and
b. a non-formaldehyde hardener selected from the group consisting of oxazolidines, nitroalcohols, nitrones, halonitroparaffins, oxazines, azaadamantanes, hexamethylenetetramine salts, nitroamines, imidazolidines, triazines, nitrooxazolidines, and imidazolidine-oxazolidine hybrids; and

ii) a fibrous substrate.

2. The composition of claim 1 wherein the resin system further comprises an additional component selected from the group consisting of internal release agents, inert solvents, reactive diluents, fillers and colorants.

3. The composition of claim 2 wherein the inert solvent is selected from the group consisting of lower alcohols, glycols, glycol derivatives, esters, water and benzyl alcohol.

4. The composition of claim 2 wherein the reactive diluent is selected from the group consisting of phenolic monomers, furfural and furfuryl alcohol.

5. The composition of claim 1 wherein the non-formaldehyde hardener comprises an oxazolidine mixed with a nitroalcohol.

6. The composition of claim 2 wherein the resin system is comprised of:
a. 45-85% by weight of novolac resin;
b. 15-55% by weight of non-formaldehyde hardener;
c. 0-6% by weight of internal release agent;
d. 0-30% by weight of inert solvents;
e. 0-50% by weight of reactive diluent;
f. 0-40% by weight of filler; and
wherein the formulated resin system has a viscosity <1MM cps at 25° C.

7. The composition of claim 1 wherein the non-formaldehyde hardener is ethyl-1-aza-3,7-dioxabicyclo[3.3.0]octane.

8. The composition of claim 1 wherein the fibrous substrate is a mat.

9. The composition of claim 1 wherein the fibrous substrate is a fiber.

10. The composition of claim 1 wherein the fibrous substrate is glass roving.

11. The composition of claim 1 wherein the fibrous substrate is selected from the group consisting of glass, carbon, basalt, graphite, synthetic fibers, and synthetic mats.

12. The composition of claim 1 which is suitable for use in pultrusion processing or filament winding.